CN114620758B - Preparation method of copper oxide modified iron-based Prussian blue positive electrode material - Google Patents
Preparation method of copper oxide modified iron-based Prussian blue positive electrode material Download PDFInfo
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- prussian blue
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- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 42
- 229960003351 prussian blue Drugs 0.000 title claims abstract description 42
- 239000013225 prussian blue Substances 0.000 title claims abstract description 42
- -1 copper oxide modified iron Chemical class 0.000 title claims abstract description 30
- 239000005751 Copper oxide Substances 0.000 title claims abstract description 25
- 229910000431 copper oxide Inorganic materials 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000003756 stirring Methods 0.000 claims abstract description 27
- 238000001035 drying Methods 0.000 claims abstract description 26
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 22
- 239000008367 deionised water Substances 0.000 claims abstract description 20
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 20
- 239000002131 composite material Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 16
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 235000017557 sodium bicarbonate Nutrition 0.000 claims abstract description 11
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 11
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 9
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims abstract description 9
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims abstract description 8
- 239000011780 sodium chloride Substances 0.000 claims abstract description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- JFSUDVTVQZUDOP-UHFFFAOYSA-N tetrasodium;iron(2+);hexacyanide;decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[Na+].[Na+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] JFSUDVTVQZUDOP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 4
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 4
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 4
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims abstract description 4
- 238000000137 annealing Methods 0.000 claims abstract description 3
- 238000000967 suction filtration Methods 0.000 claims abstract description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 31
- 239000011734 sodium Substances 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000010405 anode material Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 230000001681 protective effect Effects 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000002738 chelating agent Substances 0.000 claims description 4
- 239000002270 dispersing agent Substances 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 3
- 229940091252 sodium supplement Drugs 0.000 claims description 3
- 230000001502 supplementing effect Effects 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 2
- 229940039790 sodium oxalate Drugs 0.000 claims description 2
- 230000001133 acceleration Effects 0.000 claims 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 29
- 239000000463 material Substances 0.000 abstract description 19
- 229910052742 iron Inorganic materials 0.000 abstract description 13
- 239000001509 sodium citrate Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 2
- 230000002572 peristaltic effect Effects 0.000 abstract 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 abstract 1
- 239000002033 PVDF binder Substances 0.000 description 16
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 16
- 239000002002 slurry Substances 0.000 description 15
- 238000000576 coating method Methods 0.000 description 14
- 239000011248 coating agent Substances 0.000 description 13
- 239000003792 electrolyte Substances 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 239000006230 acetylene black Substances 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 238000003825 pressing Methods 0.000 description 8
- 238000004080 punching Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 7
- 239000011888 foil Substances 0.000 description 7
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 6
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 6
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 6
- 238000004146 energy storage Methods 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 239000010406 cathode material Substances 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 229910001415 sodium ion Inorganic materials 0.000 description 4
- 239000012535 impurity Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229910002548 FeFe Inorganic materials 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 150000004691 decahydrates Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000009766 low-temperature sintering Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000264 sodium ferrocyanide Substances 0.000 description 1
- GTSHREYGKSITGK-UHFFFAOYSA-N sodium ferrocyanide Chemical compound [Na+].[Na+].[Na+].[Na+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] GTSHREYGKSITGK-UHFFFAOYSA-N 0.000 description 1
- 235000012247 sodium ferrocyanide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 229940038773 trisodium citrate Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C3/00—Cyanogen; Compounds thereof
- C01C3/08—Simple or complex cyanides of metals
- C01C3/12—Simple or complex iron cyanides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
Abstract
The invention provides a copper oxide modified iron-based Prussian blue analogue positive electrode material and a preparation method thereof, and the specific process is as follows: ferrous sulfate heptahydrate and sodium citrate are prepared into a uniform solution A according to a certain proportion, sodium ferrocyanide decahydrate and ascorbic acid are prepared into a uniform solution B according to a certain proportion, and polyvinylpyrrolidone and sodium chloride are dissolved in deionized water to form a solution C. And simultaneously adding the solution A and the solution B into the solution C through a peristaltic pump according to the same dropping rate, coprecipitating to form the iron-based Prussian blue material, and centrifugally washing and drying. Taking out a certain amount of precursor, dispersing in deionized water, carrying out ultrasonic treatment for half an hour, adding copper chloride, sodium bicarbonate and sodium dodecyl benzene sulfonate, stirring and heating to obtain a mixture, carrying out suction filtration and washing, drying in an oven for one night, and finally, placing the mixture in a tube furnace for low-temperature annealing to obtain the copper oxide modified composite material.
Description
Technical Field
The invention relates to a copper oxide modified iron-based Prussian blue positive electrode material and a preparation method thereof, and belongs to the field of electrochemical power sources.
Background
The rapid development of large-scale smart grids and the energy demand for global sustainable development have driven the advancement of battery energy storage devices. Currently, energy storage efficiency, cost, service life and the like are the biggest problems faced by large-scale energy storage devices. In particular, extending the service life of energy storage devices is an important means of significantly reducing costs. Sodium resources take advantage of reserves and costs, and also have a relatively considerable energy density, so sodium ion batteries are considered to be the best option for achieving large-scale energy storage, while positive electrode materials are critical to the performance of the battery.
Iron-based Prussian blue sodium salt material (Na x FeFe(CN) 6 Abbreviated as Fe-PB) has a three-dimensional open framework structure, a large ion tunnel structure, which is advantageous for transportation and storage of alkali metal ions. In addition, fe-PB has two redox active sites with a higher theoretical capacity (170 mAh g -1 ). Therefore, prussian blue material is used as sodium ionThe sub-cell positive electrode material is very advantageous. However, during the synthesis, the coordinated water easily enters the Prussian blue frame and occupies a certain sodium storage site, and a large amount of Fe (CN) is generated 6 Defects, which can lead to a structure that is susceptible to failure during cycling. Thus, the cyclic performance and low capacity of Prussian blue-based materials limit their practical application. Therefore, the modified iron-based Prussian blue anode material is modified by introducing the copper oxide, the copper oxide coating layer can reduce the contact between Fe-PB and electrolyte, inhibit the occurrence of side reaction between active substances and the electrolyte, stabilize the material structure, improve the migration rate of sodium ions and effectively improve the electrochemical performance of Fe-PB.
Disclosure of Invention
The invention aims to provide a copper oxide modified iron-based Prussian blue positive electrode material Na x FeFe(CN) 6 @CuO (labeled Fe-PB@CuO). The related synthetic raw material of the Fe-PB@CuO Prussian blue cathode material is ferrous sulfate heptahydrate FeSO 4 •7H 2 Trisodium citrate O, dihydrate C 6 H 5 Na 3 O 7 •2H 2 Sodium ferrocyanide O, decahydrate Na 4 Fe(CN) 6 •10H 2 O, ascorbic acid, sodium chloride NaCl, polyvinylpyrrolidone (K88-96) PVP, copper chloride CuCl 2 Sodium bicarbonate NaHCO 3 And sodium dodecyl benzene sulfonate SDBS. The preparation method comprises the following steps:
a modification method of a copper oxide modified iron-based Prussian blue positive electrode material comprises the following steps:
(1) Dissolving ferric salt and a chelating agent in deionized water to form a mixed solution A; sodium ferrocyanide decahydrate and ascorbic acid are dissolved in deionized water to form a solution B, and a dispersing agent polyvinylpyrrolidone and a sodium supplementing agent are dissolved in deionized water to form a solution C;
(2) Dropping solution A and solution B into solution C at the same time, adding the solution A and solution B into solution C at the same time 2 Stirring while heating in the atmosphere until the dripping is completed, stirring, aging, centrifuging, washing and drying to obtain a precipitate D precursor;
(3) Dispersing the precursor of the precipitate D obtained in the step (2) in deionized water, stirring, performing ultrasonic treatment, adding copper chloride, sodium bicarbonate and sodium dodecyl benzene sulfonate, performing water bath reaction under stirring, performing suction filtration, and drying to obtain a composite material;
(4) Transferring the composite material in the step (3) into a tube furnace, and heating to 180-250 ℃ under the condition of taking nitrogen as a shielding gas o And C, preserving heat by 1-6 h, and cooling to room temperature to obtain the copper oxide modified iron-based Prussian blue anode material, namely Fe-PB@CuO.
Stirring the Fe-PB@CuO anode material and acetylene black and polyvinylidene fluoride (PVDF) into slurry, coating the slurry on an aluminum foil, and drying, film punching and film pressing to prepare the pole piece.
In the step (1), the ferric salt is at least one of ferrous sulfate heptahydrate, ferrous chloride or ferrous acetate; the molar ratio of the ferric salt to the chelating agent is 1:5-10.
The molar ratio of the sodium ferrocyanide decahydrate to the ferric salt in the step (1) is 1:0.6-1.5.
The sodium supplement in the step (1) is sodium chloride NaCl and sodium carbonate Na 2 CO 3 Sodium acetate CH 3 COONa, sodium oxalate Na 2 C 2 O 4 Sodium nitrate NaNO 3 At least one of them.
The mass ratio of the polyvinylpyrrolidone to the sodium supplementing agent is 1-1.5:2.5-3.
In the step (2), the dropping speed of the solution A and the solution B is controlled to be 0.1-0.2 ml/min, and the solution A and the solution B are controlled to be N 2 Stirring speed is 450-500 rpm under atmosphere, and reaction temperature is 40-60 o C。
In the step (2), the molar ratio of the copper chloride to the sodium bicarbonate is 1:1-3, and the mass percentage of the generated copper oxide is 2-10% of that of the precursor; the addition amount of the sodium dodecyl benzene sulfonate is 0.05-0.1% of the precursor.
In the process, sodium bicarbonate is firstly hydrolyzed to generate OH - Cu in copper chloride 2+ With OH - Reaction to Cu (OH) 2 Finally at 200 o Sintering under C for 3h, cu (OH) 2 Will decompose into CuO, and the sodium dodecyl benzene sulfonate serves as a dispersant to uniformly disperse the copper oxide in the mixturePrussian blue particle surface. If sodium bicarbonate and sodium dodecylbenzenesulfonate are added in advance in the first step, the washing is performed in a centrifugal washing step in which iron-based Prussian blue particles are formed. Therefore, the iron-based Prussian blue cube particles are synthesized through the steps (1) and (2), and then copper chloride and sodium bicarbonate are added, so that copper oxide slowly grows on the surfaces of the Prussian blue particles, and a copper oxide coating layer is formed. Copper chloride can only be added in step (3), if it is added in step (1) or (2), cu is formed on the one hand 2+ Doping, on the other hand, prussian blue particles and Cu (OH) are formed 2 The CuO can not be uniformly coated on the surface of Prussian blue particles, so that the copper chloride can only be added in the step (3).
The temperature of the water bath in the step (3) is 50-80 o C, time is 1-12 h.
Step (4) the temperature rising rate in the tube furnace is 1-10 o C/min, annealing temperature of 180-250 o And C, the heat preservation time is 1-6 h.
Compared with the prior art, the Fe-PB@CuO composite material disclosed by the invention has the following obvious characteristics:
(1) The invention has the advantages of low cost of raw materials, rich iron source and copper source, simple preparation process, no need of high-temperature treatment and suitability for large-scale industrial production;
(2) 180-250 of the preparation process o The crystallization water content of the material is obviously reduced in the low-temperature heat treatment process, more space is provided for the storage of sodium ions, and the capacity of the material is improved;
(3) The copper oxide is used for modifying the iron-based Prussian blue material, and a good shielding effect is achieved in side reaction between the active material and the electrolyte.
Drawings
Figure 1 is a graph comparing XRD of samples prepared in examples 1, 2, 3 with standard cards.
FIG. 2 is a graph showing comparison of cycle performance of samples prepared in examples 3, 4 and 5.
Fig. 3 is an SEM image of the sample prepared in example 1.
Fig. 4 is an SEM image of the sample prepared in example 3.
FIG. 5 shows the sample prepared in example 1 at 20 mA g -1 1 st, 2 nd, 10 th, 50 th turn charge-discharge curve graph at current density.
FIG. 6 is a graph of the sample prepared in example 2 at 20 mA g -1 1 st, 2 nd, 10 th, 50 th turn charge-discharge curve graph at current density.
FIG. 7 is a graph of the sample prepared in example 3 at 20 mA g -1 1 st, 2 nd, 10 th, 50 th turn charge-discharge curve graph at current density.
FIG. 8 shows the results of examples 1, 2 and 3 at 20 mA g -1 Is a graph comparing cycle performance at current density.
FIG. 9 shows examples 1, 2 and 3 at 1A g -1 Is a graph comparing cycle performance at current density.
FIG. 10 is a graph of cycle performance versus composite material.
The specific embodiment is as follows:
the following is a description of embodiments to further illustrate the essential features and advantages of the present invention.
Example 1
5 mmol FeSO 4 ·7H 2 O and 25 mmol Na 3 C 6 H 5 O 7 ·2H 2 O was dissolved in 50 ml deionized water to form solution A,5 mmol Na 4 Fe(CN) 6 ·10H 2 O and 1 g C 6 H 8 O 6 Dissolving in 50 ml deionized water to form solution B;1 g polyvinylpyrrolidone PVP and 3 g NaCl are dissolved in deionized water to form a solution C; solution A and solution B were added dropwise to solution C at a rate of 10 ml/h at 50 o Dropwise stirring in the water bath, heating for 12 h until the solution becomes white suspension after dropwise adding, continuously stirring for 12 h, and aging for 24 h; then, respectively centrifugally washing with deionized water and absolute ethyl alcohol on a centrifugal machine with the rotating speed of not less than 8000 rpm/min for three times; finally, the deep blue solid is placed in a vacuum oven 120 o C, drying 24-h to obtain the product iron-based Prussian blue positive electrode material, wherein the product iron-based Prussian blue positive electrode material is marked as Fe-PB. Stirring the obtained Fe-PB anode material with acetylene black and polyvinylidene fluoride (PVDF) to obtain slurry, and coating on aluminum foilAnd drying, film punching and film pressing to prepare the positive electrode material pole piece. Sodium metal is used as a counter electrode, grade GF/D is used as a diaphragm, and 1M NaClO containing 2 wt% FEC is used 4 And (EC+DMC+EMC) (EC: DMC: EMC=1:1:1) is used for carrying out constant-current charge and discharge test on the battery assembled by the electrolyte, and the voltage range is 2.0-4.2V. FIG. 1 is a comparison of XRD of Fe-PB with standard cards, consistent with standard cards (JCPDS, no. 52-1907), without distinct impurity peaks, but at 24.2, 38.6, 49.4 o Peak separation occurs at equal positions, and the peak separation is typical monoclinic phase. FIG. 3 is an SEM image showing that Fe-PB is a smooth surface cube morphology. FIG. 5 is a graph of 20 mA g -1 The first discharge capacity can reach 134.2 mAh g at the 1 st, 2 nd, 10 th and 50 th circles of charge and discharge curve graphs of the Fe-PB positive electrode material -1 But the second round of capacity was significantly reduced (118.3 mAh g -1 ) The reason is that the first charge-discharge curve positive electrode material and the electrolyte undergo irreversible side reaction, so that an irreversible platform appears at about 4.0V. As can be seen from the comparison of the cycle performance of FIG. 8, fe-PB is at 20 mA g -1 After 50 cycles of charge and discharge at current density, the capacity is only kept at 89.3 mAh g -1 And left and right, the circulation stability is poor. As can be seen from the comparison of the cycle performance of FIG. 9, fe-PB is at 1A g -1 The current density is only 62.8 mAh g after 200 circles of circulation -1 Is poor in cyclic stability and low in capacity.
Example 2
The procedure is as in example 1 except that the dried blue powder 200 mg is dispersed in deionized water 100 ml, stirred for 10min, sonicated for 30 min, and then added with SDBS 0.1 g at 60 o Stirring under water bath C for 6 h, suction filtering, and collecting filtrate at 80 o Drying in a C oven overnight to obtain a composite material, transferring the dried material into a tube furnace, and treating with 3% under nitrogen atmosphere o The temperature rise rate of C/min is increased to 200 o And C, preserving heat 3h, and cooling to room temperature to obtain the iron-based Prussian blue positive electrode material with comparative dryness, wherein the iron-based Prussian blue positive electrode material is marked as Fe-PB-T. Stirring the obtained Fe-PB-T positive electrode material, acetylene black and polyvinylidene fluoride (PVDF) into slurry, coating the slurry on an aluminum foil, and preparing a positive electrode material pole piece through drying, film punching and film pressing. Sodium metal is used as a counter electrode, grade GF/D is used as a diaphragm, and 1M NaClO containing 2 wt% FEC is used 4 And (EC+DMC+EMC) (EC: DMC: EMC=1:1:1) is used for carrying out constant-current charge and discharge test on the battery assembled by the electrolyte, and the voltage range is 2.0-4.2V. FIG. 1 is a graph comparing XRD of Fe-PB-T with that of a standard card, consistent with that of a standard card (JCPDS, NO. 52-1907), showing no distinct impurity peaks and good crystallinity, and exhibiting a typical cubic phase. Description 200 o The low-temperature sintering of C can obviously reduce the crystallization water in the material, so that the material is converted from a monoclinic phase to a cubic phase. FIG. 6 is a graph of 20 mA g -1 The first discharge capacity can reach 135.6 mAh g under the current density of the 1 st, 2 nd, 10 th and 50 th circles of the charge-discharge curve graph of the Fe-PB-T positive electrode material -1 . As can be seen from the comparison of the cycle performance of FIG. 8, fe-PB-T was measured at 20 mA g -1 After 50 cycles of charge and discharge at current density, the capacity is only kept at 107.1 mAh g -1 And the circulation stability is good. As can be seen from the comparison of the cycle performance of FIG. 9, fe-PB-T is at 1A g -1 The current density circulates for 200 circles and has 73.4 mAh g -1 The specific capacity of (2) is good in cycle stability and high in capacity.
Example 3
The preparation procedure was as in example 1, except that 200 mg dried blue powder obtained by drying was dispersed in 100 ml deionized water, stirred for 10min, sonicated for 30 min, and then added with 20 mg CuCl 2 、40 mg NaHCO 3 And 0.1 g SDBS at 60 o Stirring under water bath C for 6 h, suction filtering, and collecting filtrate at 80 o Drying in a baking oven overnight to obtain a composite material; transferring the dried material into a tube furnace, and treating with nitrogen as protective gas at a ratio of 3 o The temperature rise rate of C/min is increased to 200 o And C, preserving heat by 3h, and cooling to room temperature to obtain the CuO modified iron-based Prussian blue positive electrode material, wherein the CuO modified iron-based Prussian blue positive electrode material is marked as Fe-PB@4% CuO. Stirring the obtained Fe-PB@4% CuO anode material, acetylene black and polyvinylidene fluoride (PVDF) into slurry, coating the slurry on an aluminum foil, and drying, film punching and film pressing to prepare an anode material pole piece. Sodium metal is used as a counter electrode, grade GF/D is used as a diaphragm, and 1M NaClO containing 2 wt% FEC is used 4 /(ec+dmc+emc) (EC: DMC: emc=1:1:1) constant current charge and discharge test, voltage, was performed for the electrolyte assembled batteryThe range is 2.0-4.2V. FIG. 1 is a graph comparing XRD of Fe-PB@4% CuO with that of a standard card, which is consistent with that of a standard card (JCPLS, NO. 52-1907), shows no obvious impurity peaks, and shows good crystallinity, and is in a typical cubic phase. FIG. 2 is a graph showing the cycle performance of composite materials with different coating amounts of CuO, wherein the Fe-PB@4% CuO cathode material is prepared at 20 mA g -1 The first discharge capacity at the current density of (2) was 143.9 mAh g -1 After 50 cycles, the specific discharge capacity is 129.8 mAh g -1 Capacity and cycling stability are all the best of the three ratios. Fig. 4 is an SEM image, and it can be seen that Fe-pb@4% CuO still maintains a cubic morphology, but its surface is rough. FIG. 7 is a graph of 20 mA g -1 The first discharge capacity can reach 143.9 mAh g under the current density of the (1 st, 2 nd, 10 th and 50 th circles of charge-discharge curve graphs of the Fe-PB@4% CuO anode material -1 The capacity is very high. As can be seen from the comparison of the cycle properties of FIG. 8, the Fe-PB@4% CuO is at 20 mA g -1 After 50 cycles of charge and discharge at current density, the capacity is still kept at 129.8 mAh g -1 And the circulation stability is good. As can be seen from the comparison of the cycle properties of FIG. 9, the Fe-PB@4% CuO is at 1 Ag -1 The current density is still 93.9 mAh g after 200 circles of circulation -1 Has good cycle stability and high capacity.
Example 4
The preparation procedure was as in example 1, except that 200 mg dried blue powder obtained by drying was dispersed in 100 ml deionized water, stirred for 10min, sonicated for 30 min, and then 10 mg CuCl was added 2 、20 mg NaHCO 3 And 0.1 g SDBS at 60 o Stirring under water bath C for 6 h, suction filtering, and collecting filtrate at 80 o Drying in a baking oven overnight to obtain a composite material; transferring the dried material into a tube furnace, and treating with nitrogen as protective gas at a ratio of 3 o The temperature rise rate of C/min is increased to 200 o And C, preserving heat by 3h, and cooling to room temperature to obtain the CuO modified iron-based Prussian blue positive electrode material, wherein the CuO modified iron-based Prussian blue positive electrode material is marked as Fe-PB@2% CuO. Stirring the obtained Fe-PB@2% CuO anode material, acetylene black and polyvinylidene fluoride (PVDF) into slurry, coating the slurry on an aluminum foil, and drying, film punching and film pressing to prepare an anode material pole piece. The metal sodium is used as a counter electrode, grade GF/D is used as a diaphragm, and the diaphragm contains 2 w1M NaClO of t.% FEC 4 And (EC+DMC+EMC) (EC: DMC: EMC=1:1:1) is used for carrying out constant-current charge and discharge test on the battery assembled by the electrolyte, and the voltage range is 2.0-4.2V. FIG. 2 is a graph showing the cycle performance of composite materials with different coating amounts of CuO, wherein the Fe-PB@2% CuO cathode material is prepared at 20 mA g -1 The initial discharge capacity at the current density of (3) was 143.4 mAh g -1 After 50 cycles, the specific discharge capacity is 122.1 mAh g -1 The coulombic efficiency can be maintained at substantially 100%.
Example 5
The preparation procedure was as in example 1, except that 200 mg dried blue powder obtained by drying was dispersed in 100 ml deionized water, stirred for 10min, sonicated for 30 min, and then 30 mg CuCl was added 2 、60 mg NaHCO 3 And 0.1 g SDBS at 60 o Stirring under water bath C for 6 h, suction filtering, and collecting filtrate at 80 o Drying in a baking oven overnight to obtain a composite material; transferring the dried material into a tube furnace, and treating with nitrogen as protective gas at a ratio of 3 o The heating rate of C/min reaches 200 o And C, preserving heat by 3h, and cooling to room temperature to obtain the CuO modified iron-based Prussian blue positive electrode material, wherein the CuO modified iron-based Prussian blue positive electrode material is marked as Fe-PB@6% CuO. Stirring the obtained Fe-PB@6% CuO anode material, acetylene black and polyvinylidene fluoride (PVDF) into slurry, coating the slurry on an aluminum foil, and drying, film punching and film pressing to prepare an anode material pole piece. Sodium metal is used as a counter electrode, grade GF/D is used as a diaphragm, and 1M NaClO containing 2 wt% FEC is used 4 And (EC+DMC+EMC) (EC: DMC: EMC=1:1:1) is used for carrying out constant-current charge and discharge test on the battery assembled by the electrolyte, and the voltage range is 2.0-4.2V. FIG. 2 is a graph showing the cycle performance of composite materials with different coating amounts of CuO, wherein the Fe-PB@6% CuO cathode material is prepared at 20 mA g -1 The initial discharge capacity at the current density of (3) was 127.9 mAh g -1 After 50 times of circulation, the specific discharge capacity is only 104.2 mAh g -1 The coulombic efficiency can be maintained at substantially 100%.
Example 6
The preparation procedure was as in example 1, except that 200 mg dried blue powder obtained by drying was dispersed in 100 ml deionized water, stirred for 10min, sonicated for 30 min, and then added with 20 mg CuCl 2 And 0.1 g SDBS at 60 o C stirring under water bathMixing with 6 h, suction filtering, filtering at 80 o Drying in a baking oven overnight to obtain a composite material; transferring the dried material into a tube furnace, and treating with nitrogen as protective gas at a ratio of 3 o The heating rate of C/min reaches 200 o And C, preserving heat 3h, and cooling to room temperature to obtain the iron-based Prussian blue positive electrode material, wherein the iron-based Prussian blue positive electrode material is marked as Fe-PB-S. And stirring the obtained Fe-PB-S positive electrode material, acetylene black and polyvinylidene fluoride (PVDF) into slurry, coating the slurry on an aluminum foil, and drying, film punching and film pressing to prepare the positive electrode material pole piece. Sodium metal is used as a counter electrode, grade GF/D is used as a diaphragm, and 1M NaClO containing 2 wt% FEC is used 4 And (EC+DMC+EMC) (EC: DMC: EMC=1:1:1) is used for carrying out constant-current charge and discharge test on the battery assembled by the electrolyte, and the voltage range is 2.0-4.2V. FIG. 10 is a graph showing the cycle performance of the composite material, with the Fe-PB-N positive electrode material at 100 mA g -1 The initial discharge capacity at the current density of (2) was 90.0 mAh g -1 After 50 cycles, the specific discharge capacity is only 67.1 mAh g -1 The capacity retention rate is very low, and the sodium bicarbonate is not added, so that the sodium bicarbonate cannot react with the copper chloride, and the coating effect cannot be achieved, therefore, the material is extremely easy to undergo side reaction with electrolyte in the circulating process, and the material cannot serve as a buffer layer for sodium ion deintercalation, so that the circulating performance of the material is extremely poor.
Example 7
The preparation procedure was as in example 1, except that 200 mg dried blue powder obtained by drying was dispersed in 100 ml deionized water, stirred for 10min, sonicated for 30 min, and then added with 20 mg CuCl 2 And 40 mg NaHCO 3 At 60 o Stirring under water bath C for 6 h, suction filtering, and collecting filtrate at 80 o Drying in a baking oven overnight to obtain a composite material; transferring the dried material into a tube furnace, and treating with nitrogen as protective gas at a ratio of 3 o The heating rate of C/min reaches 200 o And C, preserving heat 3h, and cooling to room temperature to obtain the CuO modified iron-based Prussian blue positive electrode material, wherein the iron-based Prussian blue positive electrode material is marked as Fe-PB-N. And stirring the obtained Fe-PB-N positive electrode material, acetylene black and polyvinylidene fluoride (PVDF) into slurry, coating the slurry on an aluminum foil, and drying, film punching and film pressing to prepare the positive electrode material pole piece. Sodium metal is used as a counter electrode, grade GF/D is used as a diaphragm, and 1M NaClO containing 2 wt% FEC is used 4 And (EC+DMC+EMC) (EC: DMC: EMC=1:1:1) is used for carrying out constant-current charge and discharge test on the battery assembled by the electrolyte, and the voltage range is 2.0-4.2V. FIG. 10 is a graph showing the cycle performance of the composite material, with the Fe-PB-S positive electrode material at 100 mA g -1 The initial discharge capacity at the current density of (2) was 90.9 mAh g -1 After 50 cycles, the specific discharge capacity is only 83.3 mAh g -1 Sodium dodecyl benzene sulfonate is not added as a dispersing agent, and uneven coating is easily formed in the coating process, so that the performance is deteriorated.
Claims (8)
1. The preparation method of the copper oxide modified iron-based Prussian blue positive electrode material is characterized by comprising the following steps of:
(1) Dissolving ferric salt and a chelating agent in deionized water to form a mixed solution A; sodium ferrocyanide decahydrate and ascorbic acid are dissolved in deionized water to form a solution B, and a dispersing agent polyvinylpyrrolidone and a sodium supplementing agent are dissolved in deionized water to form a solution C;
(2) Dropping solution A and solution B into solution C at the same time, adding the solution A and solution B into solution C at the same time 2 Stirring while heating in the atmosphere until the dripping is completed, stirring, aging, centrifuging, washing and drying to obtain a precipitate D precursor;
(3) Dispersing the precursor of the precipitate D obtained in the step (2) in deionized water, stirring, carrying out ultrasonic treatment, adding copper chloride, sodium bicarbonate and sodium dodecyl benzene sulfonate, wherein the molar ratio of the copper chloride to the sodium bicarbonate is 1:1-3, the mass percent of the generated copper oxide is 2-10% of that of the precursor, the adding amount of the sodium dodecyl benzene sulfonate is 0.05-0.1% of that of the precursor, carrying out water bath reaction under stirring, carrying out suction filtration, and drying to obtain the composite material;
(4) Transferring the composite material in the step (3) into a tube furnace, heating to 180-250 ℃ under the condition of taking nitrogen as a protective gas, preserving heat for 1-6 h, and cooling to room temperature to obtain the copper oxide modified iron-based Prussian blue anode material.
2. The method for preparing a copper oxide modified iron-based Prussian blue positive electrode material according to claim 1, wherein in the step (1), the iron salt is at least one of ferrous sulfate heptahydrate, ferrous chloride or ferrous acetate; the molar ratio of the ferric salt to the chelating agent is 1:5-10.
3. The method for preparing the copper oxide modified iron-based Prussian blue positive electrode material according to claim 1, wherein the molar ratio of sodium ferrocyanide decahydrate to ferric salt in the step (1) is 1:0.6-1.5.
4. The method for preparing the copper oxide modified iron-based Prussian blue positive electrode material according to claim 1, wherein the sodium supplement agent in the step (1) is sodium chloride NaCl or sodium carbonate Na 2 CO 3 Sodium acetate CH 3 COONa, sodium oxalate Na 2 C 2 O 4 Sodium nitrate NaNO 3 At least one of them.
5. The method for preparing the copper oxide modified iron-based Prussian blue positive electrode material according to claim 1, wherein the mass ratio of polyvinylpyrrolidone to sodium supplement agent is 1-1.5:2.5-3.
6. The method for preparing a copper oxide modified iron-based Prussian blue positive electrode material according to claim 1, wherein in the step (2), the drop acceleration of the solution A and the solution B is controlled to be 0.1-0.2 ml/min, and the drop acceleration of the solution A and the solution B is controlled to be N 2 Stirring speed is 450-500 rpm under atmosphere, and reaction temperature is 40-60 o C。
7. The method for preparing the copper oxide modified iron-based Prussian blue positive electrode material according to claim 1, wherein the water bath in the step (3) has a temperature of 50 to 80 o C, time is 1-12 h.
8. The method for preparing the copper oxide modified iron-based Prussian blue positive electrode material according to claim 1, wherein the heating rate in the tube furnace in the step (4) is 1-10 o C/min, annealing temperature of 180-250 o And C, the heat preservation time is 1-6 h.
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