CN109546117A - Laminated metal organic phosphate frame sodium ion positive electrode and preparation method thereof - Google Patents
Laminated metal organic phosphate frame sodium ion positive electrode and preparation method thereof Download PDFInfo
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- CN109546117A CN109546117A CN201811377465.3A CN201811377465A CN109546117A CN 109546117 A CN109546117 A CN 109546117A CN 201811377465 A CN201811377465 A CN 201811377465A CN 109546117 A CN109546117 A CN 109546117A
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- positive electrode
- sodium ion
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- ion positive
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- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 131
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 131
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 109
- 239000002184 metal Substances 0.000 title claims abstract description 107
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 66
- 239000010452 phosphate Substances 0.000 title claims abstract description 65
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 71
- 239000006258 conductive agent Substances 0.000 claims abstract description 34
- 239000011734 sodium Substances 0.000 claims abstract description 31
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 23
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract 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 abstract description 17
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 17
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 238000005406 washing Methods 0.000 claims abstract description 15
- 239000013078 crystal Substances 0.000 claims abstract description 4
- 230000020477 pH reduction Effects 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002041 carbon nanotube Substances 0.000 claims description 11
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910021389 graphene Inorganic materials 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- ZDYUUBIMAGBMPY-UHFFFAOYSA-N oxalic acid;hydrate Chemical class O.OC(=O)C(O)=O ZDYUUBIMAGBMPY-UHFFFAOYSA-N 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 4
- 229910021542 Vanadium(IV) oxide Inorganic materials 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 239000006210 lotion Substances 0.000 claims description 3
- GRUMUEUJTSXQOI-UHFFFAOYSA-N vanadium dioxide Chemical group O=[V]=O GRUMUEUJTSXQOI-UHFFFAOYSA-N 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 12
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000001914 filtration Methods 0.000 abstract description 5
- 238000001035 drying Methods 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract description 2
- 239000007774 positive electrode material Substances 0.000 abstract 5
- 238000009776 industrial production Methods 0.000 abstract 1
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 abstract 1
- 239000002244 precipitate Substances 0.000 abstract 1
- 239000012621 metal-organic framework Substances 0.000 description 28
- 238000002156 mixing Methods 0.000 description 10
- 230000002441 reversible effect Effects 0.000 description 10
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 6
- -1 Li+ Chemical class 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 235000002639 sodium chloride Nutrition 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- RLXDCJUIXHSXQD-UHFFFAOYSA-N oxalic acid;hydrate Chemical compound O.OC(=O)C(O)=O.OC(=O)C(O)=O RLXDCJUIXHSXQD-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 239000013110 organic ligand Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- CFVBFMMHFBHNPZ-UHFFFAOYSA-N [Na].[V] Chemical compound [Na].[V] CFVBFMMHFBHNPZ-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 150000003016 phosphoric acids Chemical class 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 229940005657 pyrophosphoric acid Drugs 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910000319 transition metal phosphate Inorganic materials 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910004761 HSV 900 Inorganic materials 0.000 description 1
- 229910020657 Na3V2(PO4)3 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011066 ex-situ storage Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052816 inorganic phosphate Inorganic materials 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- WQEVDHBJGNOKKO-UHFFFAOYSA-K vanadic acid Chemical compound O[V](O)(O)=O WQEVDHBJGNOKKO-UHFFFAOYSA-K 0.000 description 1
- 239000002699 waste material 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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
层状金属有机磷酸盐框架钠离子正极材料及其制备方法，所述正极材料是由金属有机磷酸盐框架钠离子正极材料中掺杂碳导电剂而成的层状材料；所述金属有机磷酸盐框架钠离子正极材料的单晶分子式为：C2H10Na2O16P2V2，该分子结构属于空间群为手性非心空间群的单斜晶系结构。所述方法为：（1）将钒源加入水中，分散后，再加入磷酸、二水合草酸，搅拌，加入钠源，分散均匀；（2）水热反应，过滤，洗涤沉淀，干燥，得Na‑MOF材料；（3）与碳导电剂混合，研磨，即成。本发明正极材料放电克容量高，倍率性能好，循环性能、库伦效率稳定；本发明方法合成的温度低，操作简单，成本低，可控性强、重复性好，适宜于工业化生产。
A layered metal organic phosphate framework sodium ion positive electrode material and a preparation method thereof, the positive electrode material is a layered material formed by doping a metal organic phosphate framework sodium ion positive electrode material with a carbon conductive agent; the metal organic phosphate The single crystal molecular formula of the framework sodium ion positive electrode material is: C 2 H 10 Na 2 O 16 P 2 V 2 , and the molecular structure belongs to the monoclinic crystal system with the space group of chiral non-central space group. The method is as follows: (1) adding a vanadium source into water, after dispersion, adding phosphoric acid and oxalic acid dihydrate, stirring, adding a sodium source, and dispersing evenly; (2) hydrothermally reacting, filtering, washing the precipitate, and drying to obtain Na ‑MOF material; (3) Mix with carbon conductive agent, grind and serve. The positive electrode material of the invention has high discharge gram capacity, good rate performance, stable cycle performance and coulombic efficiency; the method of the invention has low synthesis temperature, simple operation, low cost, strong controllability and good repeatability, and is suitable for industrial production.
Description
Technical field
The present invention relates to a kind of sodium ion positive electrodes and preparation method thereof, and in particular to a kind of laminated metal organic phosphoric acid
Salt frame sodium ion positive electrode and preparation method thereof.
Background technique
In recent years, with the fast development in the fields such as electronic equipment, electric tool, small power electric electrical automobile, high energy is studied
Effect, resourceful and environmental-friendly energy storage material are the necessary conditions that human society realizes sustainable development.To meet rule
Mould huge market demand, it is far from being enough for only relying on the performance measures battery material such as energy density, charge-discharge magnification.
New organic materials and metal-organic framework material (MOF) are also shown as sodium ion battery electrode material
Potential application foreground.Compared with current positive electrode, MOF material is to be difficult to greatly as the biggest obstacle of sodium-ion battery material
Batch production and the isolation at redox metal center and skeleton.These disadvantages, which become, hinders MOF material as sodium ion
Cell positive material is commercialized the main reason for process.Based on this reason, the energy-storage property of New Phosphorus hydrochlorate hybrid material is just
With good cycle, the higher feature of high power charging-discharging capacity.
CN108172831A discloses type graphene carbon cladding vanadium phosphate sodium material and preparation method thereof and as sodium
The application of ion battery positive electrode, be by anionic surfactant and phosphorus source, hydrocarbon mixture, vanadium source and sodium source successively
Ball milling mixing obtains vanadium phosphate sodium presoma, is placed in protective atmosphere and calcines acquisition, and this measure improves the stability of material,
Improve the chemical property of positive electrode.But since material needs carry out high-temperature calcination in protective atmosphere, thus energy consumption compared with
Greatly, higher cost, it is suppressed that its business is used.
CN107195886 A discloses a kind of pyrophosphoric acid vanadium sodium@carbon composite anode material, preparation and application, be by
Hydro-thermal reaction is carried out comprising the solution in carbon source and vanadium source, hydro-thermal reaction product is subjected to level-one sintering, packet oxidation of coal vanadium is made；It will
It is spray-dried after packet oxidation of coal vanadium obtained, sodium source, phosphorus source wet ball grinding, obtains presoma；Presoma carries out second level and is sintered to obtain institute
The composite positive pole stated, nanoparticle surface are evenly coated carbon-coating, carbon coating are realized while by material nano, very well
The disadvantage for solving pyrophosphoric acid vanadium sodium electron conduction difference.But since material needs ball milling, spray drying, multistage calcining,
Therefore technical difficulty is big, process costs are high.
CN107317017A discloses a kind of binder free Na3V2(PO4)3The compound sodium-ion battery anode of/C and its preparation
Method is to carry out hydro-thermal reaction, and weigh phosphorus source and organic carbon source in beaker sodium source, vanadium source, deionized water, stirring is added
20min is completely dissolved to it, and the interphase liquid after natural cooling is slowly dropped to dissolved with phosphorus source and organic carbon source later
In container, 20min is stirred to solution and becomes orange-yellow, heating is concentrated into certain volume.Before carbon base body is immersed in liquid phase later
Body is driven, simultaneously high-temperature calcination obtains binder free Na for pre-burning after drying3V2(PO4)3/ C electrode, which raises the storages of the air of material
Performance, high-temperature storage performance and cycle performance.But since material making step is various, process flow is complicated, and in the process can
A large amount of waste liquids are generated, therefore pollution is larger, environmental-protecting performance is poor.
It is readily synthesized it would therefore be highly desirable to find one kind, and synthesis temperature is low, synthesis condition is simple, the preparation without presoma
With sintering, energy needed for synthesizing is not high, convenient, environmental protection sodium ion positive electrode.
Summary of the invention
The technical problem to be solved by the present invention is to overcome drawbacks described above of the existing technology, provide a kind of electric discharge gram
Capacity is high, and high rate performance is preferable, the stable laminated metal organic phosphate frame sodium ion anode material of cycle performance, coulombic efficiency
Material.
The present invention provides one kind further the technical problem to be solved is that, overcome drawbacks described above of the existing technology
Without the preparation and sintering of presoma, the temperature of synthesis is low, easy to operate, and at low cost, controllability is strong, reproducible, is suitable for
The preparation method of the laminated metal organic phosphate frame sodium ion positive electrode of industrialized production.
The technical solution adopted by the present invention to solve the technical problems is as follows: laminated metal organic phosphate frame sodium ion
Positive electrode is as adulterating stratified material made of carbonaceous conductive agent in Metal organophosphates frame sodium ion positive electrode；Institute
State the monocrystalline molecular formula of Metal organophosphates frame sodium ion positive electrode are as follows: C2H10Na2O16P2V2, which belongs to
Space group is the monoclinic structure of chiral non-heart space group.New organic materials and metal-organic framework material (MOFs) conduct
Sodium ion battery electrode material shows potential application prospect, but existing MOF material is as commercialization sodium-ion battery material
The biggest obstacle of material is: being difficult to produce in enormous quantities and the isolating problem at redox metal center and skeleton.Stratiform of the present invention
Metal organophosphates frame sodium ion positive electrode is a kind of special MOF material, is crosslinked by transition metal phosphate
The multi-dimensional spatial structure hybrid material of simple organic ligand, this structure can encapsulate various alkali in interlayer accordingly
Metal, such as Li+、Na+And K+Ion is compared to the advantages of other MOFs: inorganic phosphate salt anionic passes through enhancing transition gold
Belong to the redox property of ion, synthesis temperature needed for providing the stability to material, reduction, enhancing organic ligand are provided
Multifunctionality, and provide the possible two dimensional migration approach of more alkali metal ions, this makes with redox active gold
The synthesis of the Metal organophosphates frame material at category center is more simple, conveniently.
Preferably, the unit cell volume of the monocrystalline molecule is 620~7203, grain size is 110~140 nm, crystallization
Degree is 85~100%.
Preferably, layered Metal organophosphates frame sodium ion positive electrode is in laminar nano chip architecture, nanometer
The width of piece is 1~20 μm.Layered Metal organophosphates frame sodium ion positive electrode can produce after framework composition
Raw HPO4 2-、C2O4 2-Group, to form stratiform three-dimensional structure.
Preferably, the doping of the carbonaceous conductive agent is the 2 of Metal organophosphates frame sodium ion positive electrode quality
More preferable 5~15%)~20%(.Material of the present invention is to be doped into Metal organophosphates frame material by carbonaceous conductive agent to be formed, by
Have the characteristics that high-specific surface area, high porosity, low-density in MOF material, thus there is outstanding adsorptivity, carbonaceous conductive agent can
To be adsorbed in material well；The doping of carbonaceous conductive agent can obtain stronger electric conductivity, so that composite material exhibits go out than former
The better sodium memory capacity of beginning sample；And the doping of carbonaceous conductive agent is alternatively arranged as the buffer of volume change during sodium recycles, from
And bring better energy stores；In addition, carbonaceous conductive agent is polished, there is a small amount of carbon granules that can connect with the porous structure of MOF material
Branch forms the multistage pore structure in anode, is V in material3+Aoxidize the VO generated2Equal particles and carbon-coating (being similar to shell) provide
More attachment sites promote integrally-built stability to promote the transfer of electronics and ion.Therefore, material of the present invention
After material with carbonaceous conductive agent by being coated, its electric conductivity is enhanced, the diffusion coefficient of material is increased, to increase material work
For the circulation and high rate performance of sodium-ion battery.
Preferably, the partial size for the carbonaceous conductive agent adulterated in the nanometer sheet is 0.02~0.20 μm.
Preferably, the carbonaceous conductive agent is one or more of carbon nanotube, graphene or conductive black etc..
Preferably, the carbonaceous conductive agent is first carrying out acidification using preceding, method particularly includes: carbonaceous conductive agent is added mixed
It closes in acid, at normal temperature, carries out ultrasonic disperse, after being cooled to room temperature, be diluted with water, then filtered with miillpore filter, washed
It washs, repeating aforesaid operations to water lotion is neutrality, is finally dried under vacuum to constant weight, obtains acidification carbonaceous conductive agent.
Preferably, the mixed acid is mixed by the concentrated sulfuric acid and concentrated nitric acid with 2~4:1 of volume ratio.The concentrated sulfuric acid
Mass fraction is 90~98%, and the mass fraction of concentrated nitric acid is 60~68%.
Preferably, the mass volume ratio (g/mL) of the carbonaceous conductive agent and mixed acid is 0.1~0.3:100.
Preferably, the power of the ultrasonic disperse is 100~600W, and the time is 3~5h.
It preferably, is 3~5 times of mixed acid volume for the volume of diluted water.
Preferably, the aperture of the miillpore filter is 0.4~0.5 μm.
Preferably, the vacuum drying temperature is 80~100 DEG C.
It is as follows that the present invention further solves technical solution used by its technical problem: laminated metal organic phosphate frame
The preparation method of sodium ion positive electrode, comprising the following steps:
(1) vanadium source is added to the water, after being dispersed with stirring, adds phosphoric acid and two oxalic acid hydrates, stirred, sodium source is added, ultrasound is extremely
It is uniformly dispersed, obtains mixed solution A；
(2) mixed solution A obtained by step (1) being placed in closed reactor and carries out hydro-thermal reaction, filtered, washing precipitating is dry,
Obtain Na-MOF material；
(3) Na-MOF material obtained by step (2) is mixed with carbonaceous conductive agent, grinds, obtains laminated metal organic phosphate frame sodium
Ion positive electrode.
The thinking of the method for the present invention is first controlled syntheses C2H2Na2O14P2V2(hereinafter referred to as Na-MOF) material, then use
Carbonaceous conductive agent is doped into Na-MOF material by the method for ex situ mechanical doping, to form the stronger sodium ion of electric conductivity
Positive electrode.
Preferably, in step (1), vanadium and the molal volume of water ratio (mmol/mL) are 0.2~1.0 in the vanadium source:
1.If vanadium excessive concentration is too low, all will be difficult to form stable structure, pure MOPOF material.
Preferably, in step (1), the vanadium source is vanadium dioxide and/or vanadic anhydride etc..
Preferably, in step (1), the mass fraction of the phosphoric acid is 83~98%.
Preferably, in step (1), the speed being dispersed with stirring is more preferable 110~250 r/ of 100~400 r/min(
Min), the time being dispersed with stirring is the more preferable 7~20min of 5~30min().
Preferably, in step (1), the molar ratio of vanadium is 5~50:0.5 in the phosphoric acid, two oxalic acid hydrates and vanadium source
More preferable 10~the 15:1 of~5.0:1(~2:1).Phosphoric acid used in the method for the present invention also has other than as reactant
The effect for adjusting pH value, the prepared NA-MOF best performance under the molar ratio.
Preferably, in step (1), the molar ratio of sodium element and vanadium in vanadium source is 0.1~4.0:1 in the sodium source
(more preferable 1~3:1).If will lead to remaining side reaction generation not in the range, polluting target product.
Preferably, in step (1), the sodium source is one or more of sodium hydroxide, sodium bicarbonate or sodium chloride etc..
Preferably, in step (1), the power of the ultrasound is the more preferable 200~500W of 100~600W(), when ultrasonic
Between be the more preferable 5~50min of 1~100min().
Preferably, in step (2), 20~70%(that the volume of the mixed solution A accounts for closed reactor volume is more preferable
25~40%).
Preferably, in step (2), the temperature of the hydro-thermal reaction be 90~180 DEG C (more preferable 95~160 DEG C, more into one
Preferably 100~140 DEG C of step), the time of hydro-thermal reaction is the more preferable 36~72h of 24~80h().Oxalate be connected to phosphate radical with
Vanadic acid root forms layer structure material, ultimately forms Metal organophosphates frame material (MOPOF), this is one kind by transition
Metal phosphate is crosslinked the multi-dimensional spatial structure hybrid material of simple organic ligand, and this structure can seal accordingly in interlayer
Fill various alkali metal (such as Li+、Na+And K+) ion.Under the temperature and time, it is more advantageous to the growth of material.
Preferably, in step (2), the washing refers to deionized water and the successive cross washing of ethyl alcohol, the number of washing
>=3 times.The purpose of washing is by remaining reactant washes clean.
Preferably, in step (2), the temperature of the drying is 180~220 DEG C, and the dry time is 8~18h.
Preferably, in step (3), the dosage of the carbonaceous conductive agent be Na-MOF quality of materials 2~20%(more preferable 5~
15%).
Preferably, in step (3), the time of the grinding is the more preferable 25~40min of 20~60min().
Beneficial effects of the present invention are as follows:
(1) laminated metal organic phosphate frame sodium ion positive electrode of the present invention is assembled into sodium-ion battery, 2.5~
In 4.5V voltage range, in 0.1C(11.6mA/g) under current density, the gram volume that discharges for the first time may be up to 63.1mAh/g, coulomb
Stabilised efficiency, after recycling 30 times, electric discharge gram volume may be up to 60.6mAh/g, and electric discharge gram volume conservation rate may be up to 98.1%；
Illustrate that there is the battery that laminated metal organic phosphate frame sodium ion positive electrode of the present invention is assembled preferable electric discharge gram to hold
Amount and outstanding cyclical stability；
(2) laminated metal organic phosphate frame sodium ion positive electrode of the present invention is assembled into sodium-ion battery, 2.5~
In 4.5V voltage range, under 0.1C current density, the gram volume that discharges for the first time may be up to 62.2mAh/g, and coulombic efficiency is stablized；?
Under 0.3C current density, the gram volume that discharges is up to 52.0mAh/g；Under 0.5C current density, electric discharge gram volume is reachable
48.5mAh/g；Under 1C current density, the gram volume that discharges is up to 42.1mAh/g；Under 2C current density, electric discharge gram volume can
Up to 36.0mAh/g, illustrate battery that laminated metal organic phosphate frame sodium ion positive electrode of the present invention is assembled have compared with
Good high rate performance；
(3) the method for the present invention is not necessarily to the preparation and sintering of presoma, and the temperature of synthesis is low, easy to operate, at low cost, controllability
By force, reproducible, it is suitable for industrialized production；
(4) cathode material structure of the present invention is novel, can provide thinking for research in future Metal organophosphates frame material, open up
Thinking is opened up, there is significant scientific research value.
Detailed description of the invention
The structural schematic diagram of 1 laminated metal organic phosphate frame sodium ion positive electrode of Fig. 1 embodiment of the present invention；
Fig. 2 is the XRD refine figure of 1 laminated metal organic phosphate frame sodium ion positive electrode of the embodiment of the present invention；
Fig. 3 is the IR figure of 1 laminated metal organic phosphate frame sodium ion positive electrode of the embodiment of the present invention；
Fig. 4 is the SEM figure of 1 laminated metal organic phosphate frame sodium ion positive electrode of the embodiment of the present invention；
Fig. 5 is the TEM figure of 1 laminated metal organic phosphate frame sodium ion positive electrode of the embodiment of the present invention；
Fig. 6 is 1 laminated metal organic phosphate frame sodium ion positive electrode of the embodiment of the present invention and 1 gained Na-MOF of comparative example
The discharge cycle performance figure of material；
Fig. 7 is 1 laminated metal organic phosphate frame sodium ion positive electrode of the embodiment of the present invention and 1 gained Na-MOF of comparative example
The discharge-rate performance chart of material.
Specific embodiment
Below with reference to embodiment and attached drawing, the invention will be further described.
The mass fraction of phosphoric acid used in the embodiment of the present invention is 85%, density 1.874g/mL；Reference example of the present invention
Or carbonaceous conductive agent carbon nanotube, graphene, conductive black used in embodiment are purchased from Aladdin company；Reference example of the present invention
The mass fraction of the used concentrated sulfuric acid is 98%, and the mass fraction of concentrated nitric acid is 68%；Reference example of the present invention or embodiment are made
Chemical reagent is obtained by routine business approach unless otherwise specified.
Reference example 1
Carbonaceous conductive agent used in the embodiment of the present invention is first carrying out acidification using preceding, method particularly includes: 0.2g carbon is led
The 100mL(concentrated sulfuric acid is added in electric agent and concentrated nitric acid is mixed with volume ratio 3:1) in mixed acid, at normal temperature, under 300W, into
Row ultrasonic disperse 4h after being cooled to room temperature, adds 400mL water to dilute, is then filtered with the miillpore filter that aperture is 0.45 μm,
Washing, repeating aforesaid operations to water lotion is neutrality, finally at 90 DEG C, is dried under vacuum to constant weight, obtains acidification carbonaceous conductive agent.
Laminated metal organic phosphate frame sodium ion positive electrode embodiment 1
Layered Metal organophosphates frame sodium ion positive electrode is by Metal organophosphates frame sodium ion anode
Stratified material made of dopant acid carbon nano tube in material；The list of the Metal organophosphates frame sodium ion positive electrode
Brilliant molecular formula are as follows: C2H10Na2O16P2V2, which belongs to the monoclinic structure that space group is chiral non-heart space group；Institute
The unit cell volume for stating monocrystalline molecule is 683.949823, grain size is 131.6 nm, crystallinity 87.17%；It is layered
Metal organophosphates frame sodium ion positive electrode is in laminar nano chip architecture, and the width of nanometer sheet is 1~5 μm；The acid
The doping of carbon nano tube is the 5% of Metal organophosphates frame sodium ion positive electrode quality；It is adulterated in the nanometer sheet
Acidification carbon nanotube partial size be 0.02~0.10 μm.Layered Metal organophosphates frame sodium ion positive electrode
Structural schematic diagram is as shown in Figure 1.
As shown in Fig. 2, laminated metal of embodiment of the present invention organic phosphate frame sodium ion positive electrode belongs to space group
It is C for the monoclinic structure of chiral non-heart space group2H10Na2O16P2V2Pure phase, detailed detection data are as shown in table 1.
The crystal data and structural information table of 1 laminated metal organic phosphate frame sodium ion positive electrode embodiment 1 of table
As shown in figure 3, in the organic phosphate frame sodium ion positive electrode of laminated metal of the embodiment of the present invention, with V=O and V-O key
Relevant characteristic peak appears in 973 cm-1With 484 cm-1, and appear in 1093 cm-1、1041 cm-1And 1070cm-1Feature
Peak is then HPO4 2-Antisymmetry stretching vibration mode；Oxalate group (C2O4 2-) antisymmetry and symmetrical C=O stretching vibration band
Appear in 1689 cm-1And 1365cm-1, show the chelating bidentate bridging coordination mode of oxalato ligand.
As shown in figure 4, laminated metal of embodiment of the present invention organic phosphate frame sodium ion positive electrode is integrally in stratiform
Nanometer chip architecture, nanometer sheet width are 1~5 μm.
As shown in figure 5, in the nanometer sheet of laminated metal of embodiment of the present invention organic phosphate frame sodium ion positive electrode
Doping wrapped up carbon nanotube it is ground made of carbon granules, partial size be 0.02~0.10 μm.
The preparation method embodiment 1 of laminated metal organic phosphate frame sodium ion positive electrode
(1) 595.9mg vanadic anhydride (3.27mmol) is added in 10mL deionized water, in the mixing speed of 120 r/min
Under, after being dispersed with stirring 15min, bis- oxalic acid hydrate of 4.1mL phosphoric acid (66.64mmol) and 824.1mg (6.54 mmol) is added,
524.6 mg sodium hydroxides (13.1mmol) are added in stirring, and at 300W, it is molten to obtain 15mL mixing to being uniformly dispersed by ultrasonic 10min
Liquid A；
(2) 15mL mixed solution A obtained by step (1) is placed in 50mL closed reactor, at 120 DEG C, carries out hydro-thermal reaction
72h, filtering are precipitated 3 times with deionized water and the successive cross washing of ethyl alcohol, and at 180 DEG C, dry 12h obtains Na-MOF material
23.6g；
(3) 0.03g Na-MOF material obtained by step (2) is mixed with 0.0015g acidification carbon nanotube, is ground with agate mortar
30min obtains laminated metal organic phosphate frame sodium ion positive electrode.
Battery assembly: 0.03g the present embodiment laminated metal organic phosphate frame sodium ion positive electrode work is weighed respectively
For positive electrode, 0.0125g acetylene black (SP) is added and makees conductive agent, 0.0075g PVDF(HSV-900) make binder, sufficiently grind
After mill, 2mL NMP dispersion mixing is added, after sizing mixing uniformly, anode pole piece is made in slurry on the aluminium foil of 16 μ m-thicks, in anaerobism hand
Using metallic sodium piece as cathode in casing, with glass fibre Whatman GF/D pcs model diaphragm, 1mol/L high sodium phosphate is
Electrolyte is assembled into the button cell of CR2025.In the case where voltage range is 2.5~4.5V, to the sodium-ion battery assembled
Constant current charge-discharge performance is tested.
As shown in fig. 6, the sodium-ion battery assembled is in 2.5~4.5V voltage range, under 0.1C current density, for the first time
Electric discharge reversible specific capacity can reach 63.1mAh/g, and after 30 times recycle, electric discharge reversible specific capacity is still maintained at 60.5 mAh/g,
Its capacity retention ratio is 95.9%.
As shown in fig. 7, the sodium-ion battery assembled is in 2.5~4.5V voltage range, under 0.1C current density, for the first time
Electric discharge gram volume may be up to 58.7mAh/g, and coulombic efficiency is stablized；Under 0.3C current density, electric discharge gram volume is reachable
52.0mAh/g；Under 0.5C current density, the gram volume that discharges is up to 48.5mAh/g；Under 1C current density, discharge gram volume
Up to 42.1mAh/g；Under 2C current density, the gram volume that discharges illustrates that laminated metal of the present invention is organic still up to 36.0mAh/g
The battery that phosphate frame sodium ion positive electrode is assembled has preferable high rate performance.
From the foregoing, it will be observed that laminated metal organic phosphate frame sodium ion positive electrode obtained by the embodiment of the present invention was assembled
Battery has preferable specific discharge capacity, high rate performance and outstanding cyclical stability.
Laminated metal organic phosphate frame sodium ion positive electrode embodiment 2
Layered Metal organophosphates frame sodium ion positive electrode is by Metal organophosphates frame sodium ion anode
Stratified material made of dopant acid carbon nano tube in material；The list of the Metal organophosphates frame sodium ion positive electrode
Brilliant molecular formula are as follows: C2H10Na2O16P2V2, which belongs to the monoclinic structure that space group is chiral non-heart space group；Institute
The unit cell volume for stating monocrystalline molecule is 685.63, grain size 121.5nm, crystallinity 95%；Layered metal is organic
Phosphate frame sodium ion positive electrode is in laminar nano chip architecture, and the width of nanometer sheet is 5~10 μm；The acidification carbon nanometer
The doping of pipe is the 8% of Metal organophosphates frame sodium ion positive electrode quality；The acidification carbon adulterated in the nanometer sheet
The partial size of nanotube is 0.10~0.15 μm.
Through detecting, it is hand that laminated metal of embodiment of the present invention organic phosphate frame sodium ion positive electrode, which belongs to space group,
Property non-heart space group monoclinic structure, be C2H10Na2O16P2V2Pure phase.
Through detecting, there are V=O and V-O in the organic phosphate frame sodium ion positive electrode of laminated metal of the embodiment of the present invention
Key and HPO4 2-And C2O4 2-Group shows the chelating bidentate bridging coordination mode of oxalato ligand.
Through detecting, laminated metal of embodiment of the present invention organic phosphate frame sodium ion positive electrode is integrally in laminar nano
Chip architecture, nanometer sheet width are 5~10 μm.
Through detecting, adulterated in the nanometer sheet of laminated metal of embodiment of the present invention organic phosphate frame sodium ion positive electrode
Wrapped up carbon nanotube it is ground made of carbon granules, partial size be 0.10~0.15 μm.
The preparation method embodiment 2 of laminated metal organic phosphate frame sodium ion positive electrode
(1) 298.0mg vanadic anhydride (1.64 mmol) is added in 10mL deionized water, in the mixing speed of 110 r/min
Under, after being dispersed with stirring 10min, bis- oxalic acid hydrate of 2.2mL phosphoric acid (35.76mmol) and 413.48mg (3.28 mmol) is added,
After stirring, 262.3 mg sodium hydroxides (6.56mmol) are added, at 350W, ultrasonic 30min obtains 13mL mixing to being uniformly dispersed
Solution A；
(2) 13mL mixed solution A obtained by step (1) is placed in 50mL closed reactor, at 100 DEG C, carries out hydro-thermal reaction
54h, filtering are precipitated 3 times with deionized water and the successive cross washing of ethyl alcohol, and at 200 DEG C, dry 14h obtains Na-MOF material
22.21g；
(3) 0.05g Na-MOF material obtained by step (2) is mixed with 0.004g acidification carbon nanotube, is ground with agate mortar
35min obtains laminated metal organic phosphate frame sodium ion positive electrode.
Battery assembly: with embodiment 1.In the case where voltage range is 2.5~4.5V, to the perseverance electricity of the sodium-ion battery assembled
Stream charge-discharge performance is tested.
It is detected, the sodium-ion battery assembled under 0.1C current density, is put for the first time in 2.5~4.5V voltage range
Electric reversible specific capacity can reach 62.3mAh/g, and after 30 times recycle, electric discharge reversible specific capacity is still maintained at 60.6mAh/g, hold
Measuring conservation rate is 98.1%.
It is detected, the sodium-ion battery assembled under 0.1C current density, is put for the first time in 2.5~4.5V voltage range
Electric gram volume may be up to 62.2mAh/g, and coulombic efficiency is stablized；Under 0.3C current density, the gram volume that discharges is up to 49.6mAh/
g；Under 0.5C current density, the gram volume that discharges is up to 47.3mAh/g；Under 1C current density, electric discharge gram volume is reachable
40.1mAh/g；Under 2C current density, specific discharge capacity still up to 35.1mAh/g, illustrates laminated metal organic phosphoric acid of the present invention
The battery that salt frame sodium ion positive electrode is assembled has preferable high rate performance.
From the foregoing, it will be observed that laminated metal organic phosphate frame sodium ion positive electrode obtained by the embodiment of the present invention was assembled
Battery has preferable specific discharge capacity, high rate performance and outstanding cyclical stability.
Laminated metal organic phosphate frame sodium ion positive electrode embodiment 3
Layered Metal organophosphates frame sodium ion positive electrode is by Metal organophosphates frame sodium ion anode
Stratified material made of acidifying graphite alkene is adulterated in material；The monocrystalline of the Metal organophosphates frame sodium ion positive electrode
Molecular formula are as follows: C2H10Na2O16P2V2, which belongs to the monoclinic structure that space group is chiral non-heart space group；It is described
The unit cell volume of monocrystalline molecule is 6473, grain size 130.3nm, crystallinity 92%；Layered metal organic phosphoric acid
Salt frame sodium ion positive electrode is in laminar nano chip architecture, and the width of nanometer sheet is 5~15 μm；The acidifying graphite alkene is mixed
Miscellaneous amount is the 10% of Metal organophosphates frame sodium ion positive electrode quality；The acidifying graphite alkene adulterated in the nanometer sheet
Partial size be 0.05~0.12 μm.
Through detecting, it is hand that laminated metal of embodiment of the present invention organic phosphate frame sodium ion positive electrode, which belongs to space group,
Property non-heart space group monoclinic structure, be C2H10Na2O16P2V2Pure phase.
Through detecting, there are V=O and V-O in the organic phosphate frame sodium ion positive electrode of laminated metal of the embodiment of the present invention
Key and HPO4 2-And C2O4 2-Group shows the Bidentate State mode of oxalato ligand.
Through detecting, laminated metal of embodiment of the present invention organic phosphate frame sodium ion positive electrode is integrally in laminar nano
Chip architecture, nanometer sheet width are 5~15 μm.
Through detecting, adulterated in the nanometer sheet of laminated metal of embodiment of the present invention organic phosphate frame sodium ion positive electrode
Graphene is wrapped up, partial size is 0.05~0.12 μm.
The preparation method embodiment 3 of laminated metal organic phosphate frame sodium ion positive electrode
(1) 447.0mg vanadic anhydride (2.46 mmol) is added in 10mL deionized water, in the mixing speed of 200 r/min
Under, after being dispersed with stirring 20min, bis- oxalic acid hydrate of 3.3mL phosphoric acid (53.64mmol) and 1240.4mg (9.84 mmol) is added,
After stirring, 590.3 mg sodium hydroxides (14.75mmol) are added, at 250W, it is mixed to obtain 14mL to being uniformly dispersed by ultrasonic 20min
Close solution A；
(2) 14mL mixed solution A obtained by step (1) is placed in 50mL closed reactor, at 110 DEG C, carries out hydro-thermal reaction
66h, filtering are precipitated 3 times with deionized water and the successive cross washing of ethyl alcohol, and at 195 DEG C, dry 16h obtains Na-MOF material
24.03g；
(3) 0.1g Na-MOF material obtained by step (2) is mixed with 0.01g acidifying graphite alkene, grinds 25min with agate mortar,
Obtain laminated metal organic phosphate frame sodium ion positive electrode.
Battery assembly: with embodiment 1.In the case where voltage range is 2.5~4.5V, to the perseverance electricity of the sodium-ion battery assembled
Stream charge-discharge performance is tested.
It is detected, the sodium-ion battery assembled under 0.1C current density, is put for the first time in 2.5~4.5V voltage range
Electric reversible specific capacity can reach 61.0mAh/g, and after 30 times recycle, electric discharge reversible specific capacity is still maintained at 59.3mAh/g, hold
Measuring conservation rate is 92.8%.
It is detected, the sodium-ion battery assembled under 0.1C current density, is put for the first time in 2.5~4.5V voltage range
Electric gram volume may be up to 60.7mAh/g, and coulombic efficiency is stablized；Under 0.3C current density, the gram volume that discharges is up to 46.1mAh/
g；Under 0.5C current density, the gram volume that discharges is up to 43.4mAh/g；Under 1C current density, electric discharge gram volume is reachable
39.0mAh/g；Under 2C current density, specific discharge capacity still up to 29.7mAh/g, illustrates laminated metal organic phosphoric acid of the present invention
The battery that salt frame sodium ion positive electrode is assembled has preferable high rate performance.
From the foregoing, it will be observed that laminated metal organic phosphate frame sodium ion positive electrode obtained by the embodiment of the present invention was assembled
Battery has preferable specific discharge capacity, high rate performance and outstanding cyclical stability.
Laminated metal organic phosphate frame sodium ion positive electrode embodiment 4
Layered Metal organophosphates frame sodium ion positive electrode is by Metal organophosphates frame sodium ion anode
Stratified material made of doping acidification conductive black in material；The list of the Metal organophosphates frame sodium ion positive electrode
Brilliant molecular formula are as follows: C2H10Na2O16P2V2, which belongs to the monoclinic structure that space group is chiral non-heart space group；Institute
The unit cell volume for stating monocrystalline molecule is 701.23, grain size 129.8nm, crystallinity 85%；Layered metal is organic
Phosphate frame sodium ion positive electrode is in laminar nano chip architecture, and the width of nanometer sheet is 1~10 μm；The conductive charcoal of the acidification
Black doping is the 8% of Metal organophosphates frame sodium ion positive electrode quality；The acidification adulterated in the nanometer sheet is led
The partial size of electric carbon black is 0.10~0.20 μm.
Through detecting, it is hand that laminated metal of embodiment of the present invention organic phosphate frame sodium ion positive electrode, which belongs to space group,
Property non-heart space group monoclinic structure, be C2H10Na2O16P2V2Pure phase.
Through detecting, there are V=O and V-O in the organic phosphate frame sodium ion positive electrode of laminated metal of the embodiment of the present invention
Key and HPO4 2-And C2O4 2-Group shows the chelating bidentate bridging coordination mode of oxalato ligand.
Through detecting, laminated metal of embodiment of the present invention organic phosphate frame sodium ion positive electrode is integrally in laminar nano
Chip architecture, nanometer sheet width are 1~10 μm.
Through detecting, adulterated in the nanometer sheet of laminated metal of embodiment of the present invention organic phosphate frame sodium ion positive electrode
Conductive black is wrapped up, partial size is 0.10~0.20 μm.
The preparation method embodiment 4 of laminated metal organic phosphate frame sodium ion positive electrode
(1) 610.4mg vanadium dioxide (7.36mmol) is added in 10mL deionized water, under the mixing speed of 150 r/min,
After being dispersed with stirring 7min, bis- oxalic acid hydrate of 5.38mL phosphoric acid (87.45mmol) and 1391.7mg (11.04 mmol) is added, is stirred
After mixing, it is added 430.1mg sodium chloride (7.36mmol), at 500W, ultrasonic 5min obtains 16mL mixed solution A to being uniformly dispersed；
(2) 16mL mixed solution A obtained by step (1) is placed in 50mL closed reactor, at 105 DEG C, carries out hydro-thermal reaction
48h, filtering are precipitated 4 times with deionized water and the successive cross washing of ethyl alcohol, and at 210 DEG C, dry 18h obtains Na-MOF material
23.89g；
(3) 0.06g Na-MOF material obtained by step (2) is mixed with 0.0048g acidification conductive black, is ground with agate mortar
40min obtains laminated metal organic phosphate frame sodium ion positive electrode.
Battery assembly: with embodiment 1.In the case where voltage range is 2.5~4.5V, to the perseverance electricity of the sodium-ion battery assembled
Stream charge-discharge performance is tested.
It is detected, the sodium-ion battery assembled under 0.1C current density, is put for the first time in 2.5~4.5V voltage range
Electric reversible specific capacity can reach 58.7mAh/g, and after 30 times recycle, electric discharge reversible specific capacity is still maintained at 57.2mAh/g, hold
Measuring conservation rate is 97.4%.
It is detected, the sodium-ion battery assembled under 0.1C current density, is put for the first time in 2.5~4.5V voltage range
Electric gram volume may be up to 62.4mAh/g, and coulombic efficiency is stablized；Under 0.3C current density, the gram volume that discharges is up to 43.3mAh/
g；Under 0.5C current density, the gram volume that discharges is up to 39.3mAh/g；Under 1C current density, electric discharge gram volume is reachable
34.8mAh/g；Under 2C current density, specific discharge capacity still up to 30.1mAh/g, illustrates laminated metal organic phosphoric acid of the present invention
The battery that salt frame sodium ion positive electrode is assembled has preferable high rate performance.
From the foregoing, it will be observed that laminated metal organic phosphate frame sodium ion positive electrode obtained by the embodiment of the present invention was assembled
Battery has preferable specific discharge capacity, high rate performance and outstanding cyclical stability.
Comparative example 1
Comparative example 1 and the difference of embodiment 1 are only that: being removed step (3), obtained Na-MOF material.
Battery assembly: with embodiment 1.In the case where voltage range is 2.5~4.5V, to the perseverance electricity of the sodium-ion battery assembled
Stream charge-discharge performance is tested.
As shown in fig. 6, the sodium-ion battery assembled is in 2.5~4.5V voltage range, under 0.1C current density, for the first time
Electric discharge reversible specific capacity is 59.1 mAh/g, and after 30 times recycle, electric discharge reversible specific capacity is only 19.3 mAh/g, and capacity is protected
Holdup is only 32.7 %, illustrates that its cycle performance is very poor.
As shown in fig. 7, the sodium-ion battery assembled is in 2.5~4.5V voltage range, under 0.1C current density, for the first time
Electric discharge gram volume is 61.6mAh/g；Under 2C current density, specific discharge capacity drops to 0.7mAh/g, illustrates its high rate performance
It is very poor.
From the foregoing, it will be observed that the addition of carbonaceous conductive agent can effectively improve the circulation and high rate performance of positive electrode.
Claims (10)
1. a kind of laminated metal organic phosphate frame sodium ion positive electrode, which is characterized in that be by Metal organophosphates
Stratified material made of carbonaceous conductive agent is adulterated in frame sodium ion positive electrode；The Metal organophosphates frame sodium ion is just
The monocrystalline molecular formula of pole material are as follows: C2H10Na2O16P2V2, which belongs to the monocline that space group is chiral non-heart space group
Crystal structure.
2. laminated metal organic phosphate frame sodium ion positive electrode according to claim 1, it is characterised in that: the list
The unit cell volume of brilliant molecule is 620~7203, grain size is 110~140 nm, and crystallinity is 85~100%；It is layered
Metal organophosphates frame sodium ion positive electrode is in laminar nano chip architecture, and the width of nanometer sheet is 1~20 μm.
3. laminated metal organic phosphate frame sodium ion positive electrode according to claim 1 or claim 2, it is characterised in that: institute
The doping for stating carbonaceous conductive agent is the 2~20% of Metal organophosphates frame sodium ion positive electrode quality；In the nanometer sheet
The partial size of the carbonaceous conductive agent of doping is 0.02~0.20 μm；The carbonaceous conductive agent is in carbon nanotube, graphene or conductive black
One or more；The carbonaceous conductive agent is first carrying out acidification using preceding, method particularly includes: carbonaceous conductive agent is added and is mixed
In acid, at normal temperature, ultrasonic disperse is carried out, after being cooled to room temperature, is diluted with water, is then filtered with miillpore filter, washed,
Repeating aforesaid operations to water lotion is neutrality, is finally dried under vacuum to constant weight, obtains acidification carbonaceous conductive agent；The mixed acid is by dense sulphur
Acid and concentrated nitric acid are mixed with 2~4:1 of volume ratio；The mass volume ratio of the carbonaceous conductive agent and mixed acid is 0.1~0.3:
100；The power of the ultrasonic disperse is 100~600W, and the time is 3~5h；Volume for diluted water is mixed acid volume
3~5 times；The aperture of the miillpore filter is 0.4~0.5 μm；The vacuum drying temperature is 80~100 DEG C.
4. a kind of preparation side of the layered Metal organophosphates frame sodium ion positive electrode of one of such as claims 1 to 3
Method, which comprises the following steps:
(1) vanadium source is added to the water, after being dispersed with stirring, adds phosphoric acid and two oxalic acid hydrates, stirred, sodium source is added, ultrasound is extremely
It is uniformly dispersed, obtains mixed solution A；
(2) mixed solution A obtained by step (1) being placed in closed reactor and carries out hydro-thermal reaction, filtered, washing precipitating is dry,
Obtain Na-MOF material；
(3) Na-MOF material obtained by step (2) is mixed with carbonaceous conductive agent, grinds, obtains laminated metal organic phosphate frame sodium
Ion positive electrode.
5. laminated metal organic phosphate frame sodium ion positive electrode according to claim 4, it is characterised in that: step
(1) in, vanadium and the molal volume of water ratio are 0.2~1.0:1 in the vanadium source；The vanadium source is vanadium dioxide and/or five
V 2 O；The speed being dispersed with stirring is 100~400 r/min, and the time being dispersed with stirring is 5~30min.
6. laminated metal organic phosphate frame sodium ion positive electrode according to claim 4 or 5, it is characterised in that: step
Suddenly in (1), the molar ratio of vanadium is 5~50:0.5~5.0:1 in the phosphoric acid, two oxalic acid hydrates and vanadium source；The sodium source
The molar ratio of vanadium is 0.1~4.0:1 in middle sodium element and vanadium source；The sodium source is sodium hydroxide, sodium bicarbonate or chlorination
One or more of sodium.
7. according to the layered Metal organophosphates frame sodium ion positive electrode of one of claim 4~6, feature exists
In: in step (1), the power of the ultrasound is 100~600W, and the ultrasonic time is 1~100min.
8. according to the layered Metal organophosphates frame sodium ion positive electrode of one of claim 4~7, feature exists
In: in step (2), the volume of the mixed solution A accounts for the 20~70% of closed reactor volume；The temperature of the hydro-thermal reaction
It is 90~180 DEG C, the time of hydro-thermal reaction is 24~80h.
9. according to the layered Metal organophosphates frame sodium ion positive electrode of one of claim 4~8, feature exists
In: in step (2), the washing refers to deionized water and the successive cross washing of ethyl alcohol, number >=3 time of washing；It is described dry
Dry temperature is 180~220 DEG C, and the dry time is 8~18h.
10. according to the layered Metal organophosphates frame sodium ion positive electrode of one of claim 4~9, feature exists
In: in step (3), the dosage of the carbonaceous conductive agent is the 2~20% of Na-MOF quality of materials；The time of the grinding be 20~
60min。
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