CN115108566A - Preparation method of long-life iron-based Prussian blue positive electrode material - Google Patents
Preparation method of long-life iron-based Prussian blue positive electrode material Download PDFInfo
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- CN115108566A CN115108566A CN202210711134.9A CN202210711134A CN115108566A CN 115108566 A CN115108566 A CN 115108566A CN 202210711134 A CN202210711134 A CN 202210711134A CN 115108566 A CN115108566 A CN 115108566A
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- prussian blue
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- iron
- sodium
- based prussian
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 32
- 229960003351 prussian blue Drugs 0.000 title claims abstract description 31
- 239000013225 prussian blue Substances 0.000 title claims abstract description 31
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 30
- 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 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000008367 deionised water Substances 0.000 claims abstract description 27
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 27
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 239000002270 dispersing agent Substances 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 18
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 16
- 239000010406 cathode material Substances 0.000 claims abstract description 15
- 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 12
- 239000012298 atmosphere Substances 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 9
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 239000011780 sodium chloride Substances 0.000 claims abstract description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 7
- 239000001509 sodium citrate Substances 0.000 claims abstract description 7
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims abstract description 7
- -1 Prussian blue compound Chemical class 0.000 claims abstract description 6
- 230000032683 aging Effects 0.000 claims abstract description 6
- 229960005070 ascorbic acid Drugs 0.000 claims abstract description 6
- 235000010323 ascorbic acid Nutrition 0.000 claims abstract description 6
- 239000011668 ascorbic acid Substances 0.000 claims abstract description 6
- 238000000967 suction filtration Methods 0.000 claims abstract description 6
- 239000000725 suspension Substances 0.000 claims abstract description 5
- 150000002505 iron Chemical class 0.000 claims abstract description 3
- 239000011734 sodium Substances 0.000 claims description 17
- 229910001415 sodium ion Inorganic materials 0.000 claims description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 11
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000010405 anode material Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 6
- 229940091252 sodium supplement Drugs 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000000264 sodium ferrocyanide Substances 0.000 claims description 3
- 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 claims description 3
- 235000012247 sodium ferrocyanide Nutrition 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 230000003078 antioxidant effect Effects 0.000 claims description 2
- 235000006708 antioxidants Nutrition 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 abstract description 5
- 230000002572 peristaltic effect Effects 0.000 abstract description 3
- 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 abstract description 2
- 239000002033 PVDF binder Substances 0.000 description 12
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 12
- 239000002002 slurry Substances 0.000 description 12
- 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 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- 230000004087 circulation Effects 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000006230 acetylene black Substances 0.000 description 6
- 230000004913 activation Effects 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 238000003825 pressing Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000004080 punching Methods 0.000 description 6
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical group O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- VJMAITQRABEEKP-UHFFFAOYSA-N [6-(phenylmethoxymethyl)-1,4-dioxan-2-yl]methyl acetate Chemical compound O1C(COC(=O)C)COCC1COCC1=CC=CC=C1 VJMAITQRABEEKP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
Images
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-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
-
- 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
- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a preparation method of a long-life iron-based Prussian blue positive electrode material. Dissolving Fe-containing salt and sodium citrate in deionized water to form a solution A, dissolving sodium ferrocyanide decahydrate and ascorbic acid in deionized water to form a solution B, and dissolving polyvinylpyrrolidone and sodium chloride in deionized water to form a solution C. In N 2 Under the conditions of atmosphere, heating and stirring, simultaneously adding the solution A and the solution B into the solution C through a peristaltic pump, and after the dropwise addition is finished, changing the solution into a white suspension; and continuously heating and stirring, finally aging at room temperature, sequentially centrifugally washing for a plurality of times by using deionized water and absolute ethyl alcohol, and drying in vacuum to obtain the initial iron-based Prussian blue compound. Dispersing a certain amount of initial iron-based Prussian blue compound in deionized water under the protection of inert atmosphere, adding a small amount of alcohol dispersant, and magnetically stirring for a certain timeAnd after the time, carrying out suction filtration and washing, and drying to obtain the modified iron-based Prussian blue cathode material.
Description
Technical Field
The invention relates to a long-life iron-based Prussian blue sodium ion battery positive electrode material and a preparation method thereof, belonging to the technical field of sodium ion batteries.
Background
The lithium ion battery is an important and environment-friendly energy storage device and is widely applied to portable electronic equipment, new energy automobiles, energy storage power stations and the like. With the advent of the era of electric automobiles and smart grids, the large-scale development of lithium ion batteries is restricted by the bottleneck of lithium resource shortage. Sodium reserves are abundant, widely distributed, low cost, and have similar physicochemical properties to lithium, compared to lithium, so that the research of sodium ion batteries is once again receiving extensive attention from academia and industry. Compared with the lithium ion battery, the energy density of the sodium ion battery is relatively low, so that the sodium ion battery is not suitable for the fields of portable electronic equipment and electric automobiles with high requirements on the energy density, but is suitable for the fields of low-speed electric vehicles, communication base stations, household energy storage and the like with low requirements on the energy density and sensitive cost.
The technology and technology of the sodium ion battery are very similar to those of the lithium ion battery, but the radius of sodium ions is large, so that the electrode material is difficult to embed and remove, and therefore, the search for a proper electrode material for storing sodium becomes a great challenge. Compared with the cathode material, the selection of the cathode material is more critical, and the conditions of rich raw materials, high specific capacity, high working voltage, stable structure and the like need to be met. Among various positive electrode materials of sodium ion batteries currently studied, iron-based Prussian blue (molecular formula is Na) 2 Fe[Fe(CN) 6 ]Fe-PB) positive electrode material has received wide attention because of its open frame structure favorable to sodium ion deintercalation and its advantages of environmental protection, low toxicity, low cost, etc. The specific capacity of Fe-PB is high, but the cycle performance is not ideal. According to the invention, the initial iron-based Prussian blue material synthesized by the sodium citrate assisted coprecipitation method is dispersed in a certain amount of deionized water under the protection of inert atmosphere, and a small amount of alcohol dispersant is added, so that the cycle stability of the iron-based Prussian blue positive electrode material is obviously improved.
Disclosure of Invention
The invention aims to provide a long-life iron-based Prussian blue positive electrode material prepared by a simple method. The synthesis raw materials of the long-life iron-based Prussian blue sodium ion battery positive electrode material comprise: wherein the iron-containing salt is ferrous sulfate heptahydrate FeSO 4 ·7H 2 O (or FeCl) 2 Fe (CH) acetate 3 COO) 2 ) Lemon dihydrateTrisodium citrate C 6 H 5 Na 3 O 7 •2H 2 O, sodium ferrocyanide decahydrate Na 4 Fe(CN) 6 ·10H 2 O, ascorbic acid C 6 H 8 O 6 Polyvinyl pyrrolidone PVP and sodium chloride NaCl (or sodium carbonate Na) 2 CO 3 Sodium acetate CH 3 COONa), deionized water (or distilled water, purified water, tap water).
The preparation method comprises the following steps:
one of the technical schemes of the invention provides a long-life iron-based Prussian blue positive electrode material and a preparation method thereof, wherein the preparation method comprises the following steps:
(1) dissolving a Fe-containing salt and a chelating agent sodium citrate into deionized water to prepare a solution A; dissolving a proper amount of sodium ferrocyanide and an antioxidant ascorbic acid in a proper amount of deionized water to prepare a solution B, and dissolving a dispersant polyvinylpyrrolidone and a proper amount of a sodium supplement agent in a proper amount of deionized water to obtain a solution C;
(2) in N 2 Under the conditions of atmosphere, heating and stirring, simultaneously adding the solution A and the solution B into the solution C through a peristaltic pump, and after the dropwise addition is finished, changing the solution into a white suspension; and continuously heating and stirring for 10-12h, and finally aging for 10-30h at room temperature. After the supernatant is poured out, sequentially centrifuging and washing the lower white precipitate by deionized water and absolute ethyl alcohol for several times, and drying in vacuum at the temperature of 100-140 ℃ for 10-12h to obtain a light blue initial iron-based Prussian blue compound;
(3) dispersing a certain amount of initial iron-based Prussian blue compounds in deionized water under the protection of inert atmosphere, adding a small amount of alcohol dispersant, magnetically stirring for a certain time, performing suction filtration and washing, and drying in an oven at 60-80 ℃ overnight to obtain the iron-based Prussian blue sodium ion battery anode material.
In the step (1), the iron salt is ferrous sulfate heptahydrate FeSO 4 ·7H 2 O, ferrous chloride FeCl 2 Or ferrous acetate Fe (CH) 3 COO) 2 In the above aspect, the molar ratio of the Fe-containing salt to the sodium citrate is 1:1 to 10, and more preferably 1: 5.
Ferrocyanide in step (1)Sodium sulfate Na 4 Fe(CN) 6 ·10H 2 The molar ratio of O, the transition metal salt and the ascorbic acid is 1: 0.6-1.5: 3-10.
The sodium supplement agent in the step (1) is sodium chloride NaCl and sodium carbonate Na 2 CO 3 Sodium acetate CH 3 COONa and/or COONa.
The mass ratio of the polyvinylpyrrolidone to the sodium supplement agent is 1-1.5: 5.5-7.
The dropping speed of the solution A and the solution B is controlled to be 10 ml/h, and the dropping speed is controlled to be N 2 Under the atmosphere, the stirring speed is 400-600 rpm, and the reaction temperature is 45-55 ℃.
In the step (3), the inert atmosphere is argon or nitrogen.
In the step (3), the alcohol dispersant is one or more of ethanol, ethylene glycol, isopropanol, isobutanol, n-butanol, isoamyl alcohol, cyclohexanol and the like.
And (3) sequentially centrifuging and washing the aged white precipitate for three times by using deionized water and absolute ethyl alcohol and a centrifugal speed of not less than 8000 rpm/min to obtain a clean precipitate.
The drying mode in the step (4) is vacuum drying, the temperature is 100-120 ℃, and the time is 20-30 hours.
The medicines involved are all analytically pure.
Compared with the prior art, the preparation method of the long-life iron-based Prussian blue anode material provided by the invention is simple and easy to control, the capacity and the stability of the iron-based Prussian blue anode material are improved by avoiding doping heterogeneous atoms or coating other materials or carrying out heat treatment, and the production cost is greatly reduced. According to the preparation method of the iron-based Prussian blue cathode material, higher capacity and more excellent cycling stability compared with the initial iron-based Prussian blue material can be obtained.
Drawings
Figure 1 is a comparison of XRD of samples prepared in examples 1, 2, 3 with a standard card.
Figure 2 is a comparison of XRD of the samples prepared in examples 4, 5, 6 with a standard card.
FIG. 3 shows the results of example 1 when the sample is measured at 100 mA g -1 Current density ofAnd the charging and discharging curve charts of the 1 st circle, the 5 th circle and the 50 th circle under the degree.
FIG. 4 shows the results of example 2 prepared samples at 100 mA g -1 The charge and discharge curves of the 1 st, 5 th and 50 th circles at the current density of (c).
FIG. 5 shows the results of example 3 when the sample is prepared at 100 mA g -1 The charge and discharge curves of the 1 st, 5 th and 50 th circles at the current density of (c).
FIG. 6 shows the results of example 4 at 100 mA g -1 1 st, 5 th and 50 th circles under the current density.
FIG. 7 shows the results of example 5 prepared samples at 100 mA g -1 The charge and discharge curves of the 1 st, 5 th and 50 th circles at the current density of (c).
FIG. 8 shows the results of example 6 prepared samples at 100 mA g -1 The charge and discharge curves of the 1 st, 5 th and 50 th circles at the current density of (c).
FIG. 9 is a graph comparing the cycle performance of samples prepared in examples 1, 2, 3, 4, 5, and 6.
Detailed Description
The essential features and advantages of the invention are further illustrated by the following description of the embodiments.
Example 1
Adding 5 mmol of FeSO 4 ·7H 2 O and 25 mmol Na 3 C 6 H 5 O 7 ·2H 2 O was dissolved in 50 ml of 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 of deionized water to form a solution B; dissolving 1 g of polyvinylpyrrolidone PVP and 3 g of NaCl in deionized water to form solution C; in N 2 Under the conditions of atmosphere, heating and stirring, simultaneously adding the solution A and the solution B into the solution C through a peristaltic pump, and after the dropwise addition is finished, changing the solution into a white suspension; heating and stirring are continued for 12h, and finally aging is carried out at room temperature for 24 h. After the supernatant was decanted, the lower white precipitate was washed several times by successive centrifugation with deionized water and absolute ethanol at 120 o Vacuum drying for 12h under C to obtain initial iron-based Prussian blue anode material marked as Fe-PB. Stirring the obtained Fe-PB positive electrode material with acetylene black and polyvinylidene fluoride (PVDF) to form slurry, coating the slurry on an aluminum foil, and drying, punching and pressing the film to prepare a positive electrode material pole piece. 1M NaClO containing 2 wt.% FEC and taking metallic sodium as a counter electrode and Grade GF/D as a diaphragm 4 And (EC + DMC + EMC) (EC: DMC: EMC =1:1:1) is a 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 card. It is clear that the crystallinity of Fe-PB is good and that the diffraction peaks are substantially in agreement with those of the standard card (JCPDS, number 52-1907), but at 24.16, 38.54 and 49.46 o The peak separation phenomenon appears at the position of the Fe-PB, which indicates that the Fe-PB is a typical monoclinic phase. FIG. 3 shows the Fe-PB positive electrode material at 100 mA g -1 The charge and discharge curves of the 1 st, 5 th and 50 th circles at the current density of (1), and FIG. 9 is a graph of the Fe-PB positive electrode material at 100 mA g -1 Current density of (a). Obviously, the first discharge capacity of Fe-PB can reach 148.3 mAh g -1 Capacity after 5 and 50 cycles was 114.5 mAh g -1 And 87.3 mAh g -1 (ii) a Considering the activation of the electrode, the capacity retention ratio of the 50 th circle relative to the 5 th circle was calculated to be 76.2%. As can be seen, the Fe-PB cycle stability is poor.
Example 2
200 mg of Fe-PB prepared in example 1 were dispersed in 100 ml of deionized water, magnetically stirred for 3 hours, suction-filtered and washed, and the reaction mixture was then filtered at 80 ℃ o And drying in an oven C for 12h to obtain Fe-PB-W. Stirring Fe-PB-W positive electrode material, acetylene black and polyvinylidene fluoride (PVDF) into slurry, coating the slurry on an aluminum foil, and drying, punching and pressing the film to prepare a positive electrode material pole piece. 1M NaClO containing 2 wt.% FEC and taking metallic sodium as a counter electrode and Grade GF/D as a diaphragm 4 And (EC + DMC + EMC) (EC: DMC: EMC =1:1:1) is a battery assembled by the electrolyte, and the voltage range is 2.0-4.2V. FIG. 1 is a comparison of XRD of Fe-PB-W with standard card. Obviously, the crystallinity of Fe-PB-W is good, and each diffraction peak completely corresponds to that of standard card (JCPDS, number 52-1907), and the phenomenon of Fe-PB peak splitting similar to that in example 1 does not occur, and a typical cubic structure is presented. FIG. 4 shows the Fe-PB-W positive electrode material at 100 mA g -1 1 st turn, 5 th turn at current density ofThe charge-discharge curves of the circles and the 50 th circle are shown in FIG. 9, which shows that the Fe-PB-W anode material is 100 mA g -1 Current density of (a). The first discharge capacity of Fe-PB-W is only 82.5 mAh g -1 Capacity after 5 and 50 cycles of 80.4 mAh g -1 And 77.6 mAh g -1 (ii) a In consideration of the activation of the electrode, the capacity retention ratio of the 50 th turn to the 5 th turn was calculated to be 96.5%. As can be seen, the cycling stability of Fe-PB-W is better, but the capacity is lower.
Example 3
200 mg of Fe-PB prepared in example 1 were dispersed in 100 ml of absolute ethanol, magnetically stirred for 3 h, filtered with suction, and purified at 80% o And drying in an oven C for 12h to obtain Fe-PB-E. Stirring the obtained Fe-PB-E positive electrode material with acetylene black and polyvinylidene fluoride (PVDF) to form slurry, coating the slurry on an aluminum foil, and drying, punching and pressing the film to obtain a positive electrode material pole piece. 1M NaClO containing 2 wt.% FEC and taking metallic sodium as a counter electrode and Grade GF/D as a diaphragm 4 And (EC + DMC + EMC) (EC: DMC: EMC =1:1:1) is a battery assembled by the electrolyte, and the voltage range is 2.0-4.2V. FIG. 1 is a comparison of XRD of Fe-PB-E with standard card. It is clear that Fe-PB-E shows good crystallinity with diffraction peaks substantially matching those of standard card (JCPDS, number 52-1907), but at 24.16, 38.54 and 49.46 o The peak separation phenomenon also appears at the position of the Fe-PB-E, which indicates that the Fe-PB-E is a monoclinic phase. FIG. 5 shows that the Fe-PB-E positive electrode material is 100 mA g -1 The charge and discharge curves of the 1 st, 5 th and 50 th circles at the current density of (1), and FIG. 9 is a graph showing that the Fe-PB-E positive electrode material is 100 mA g -1 Current density of (a). The first discharge capacity of Fe-PB-E is 121.5 mAh g -1 Capacity after 5 and 50 circulations is 90.4 mAh g -1 And 79.1 mAh g -1 (ii) a In consideration of the activation of the electrode, the capacity retention ratio at the 50 th turn relative to the 5 th turn was calculated to be 87.5%. As can be seen, the Fe-PB-E has better cycle stability.
Example 4
200 mg of Fe-PB prepared in example 1 were dispersed in 100 ml of deionized water under a nitrogen atmosphere, magnetically stirred for 3 hours, filtered off with suction, and the filtrate was taken at 80 degrees o Drying in a C oven for 12 hours to obtain Fe-PB-W-N 2 . Will be provided withObtaining Fe-PB-W-N 2 The positive electrode material, acetylene black and polyvinylidene fluoride (PVDF) are stirred into slurry, the slurry is coated on an aluminum foil, and a positive electrode material pole piece is manufactured through drying, membrane punching and membrane pressing. 1M NaClO containing 2 wt.% FEC and taking metallic sodium as a counter electrode and Grade GF/D as a diaphragm 4 and/(EC + DMC + EMC) (EC: DMC: EMC =1:1:1) is a battery assembled by the electrolyte to carry out constant-current charge and discharge tests, and the voltage range is 2.0-4.2V. FIG. 2 shows Fe-PB-W-N 2 XRD of (a) versus standard card. Apparently, Fe-PB-W-N 2 Shows good crystallinity, and the diffraction peaks of the crystal are basically consistent with that of a standard card (JCPDS, number 52-1907), but are at 24.16, 38.54 and 49.46 o The peak separation phenomenon also appears at the same position, which shows that Fe-PB-W-N 2 Is monoclinic phase. FIG. 6 is Fe-PB-W-N 2 The cathode material is 100 mA g -1 The charge and discharge curves of the 1 st, 2 nd and 50 th turns at the current density of (1), and FIG. 9 is a graph of Fe-PB-W-N 2 The cathode material is 100 mA g -1 Current density of (a). The first discharge capacity of Fe-PB-E is 152.7 mAh g -1 Capacity after 5 and 50 cycles of 96.3 mAh g -1 And 83.8 mAh g -1 (ii) a In consideration of the activation of the electrode, the capacity retention ratio was calculated to be 87.0% at the 50 th turn relative to the 5 th turn. Visible as Fe-PB-W-N 2 The cycling stability is superior, but the capacity is low.
Example 5
200 mg of Fe-PB prepared by example 1 were dispersed in 100 ml of deionized water, and 2 ml of isopropyl alcohol dispersant was added, followed by magnetic stirring for 3 hours, suction filtration washing, and 80 hours o And drying in an oven C for 12h to obtain Fe-PB-W-IPA. Stirring Fe-PB-W-IPA positive electrode material, acetylene black and polyvinylidene fluoride (PVDF) into slurry, coating the slurry on an aluminum foil, and drying, punching and pressing the film to prepare a positive electrode material pole piece. 1M NaClO containing 2 wt.% FEC and taking metallic sodium as a counter electrode and Grade GF/D as a diaphragm 4 and/(EC + DMC + EMC) (EC: DMC: EMC =1:1:1) is a battery assembled by the electrolyte to carry out constant-current charge and discharge tests, and the voltage range is 2.0-4.2V. FIG. 2 is a comparison of XRD of Fe-PB-W-IPA with standard card. Obviously, the crystallinity of Fe-PB-W-IPA is good, and each diffraction peak completely corresponds to that of the standard card (JCPDS, number 52-1907), and no class appearsSimilar to the peak separation of Fe-PB in example 1, a typical cubic structure is shown. FIG. 7 shows the concentration of Fe-PB-W-IPA cathode material at 100 mA g -1 The charge and discharge curves of the 1 st, 5 th and 50 th circles at the current density of (A), and FIG. 9 shows that the Fe-PB-W-IPA positive electrode material is 100 mA g/g -1 Current density of (a). The first discharge capacity of Fe-PB-W-IPA is 114.1 mAh g -1 Capacity after 5 and 50 cycles of 79.7 mAh g -1 And 68.1 mAh g -1 (ii) a In consideration of the activation of the electrode, the capacity retention ratio of the 50 th turn to the 5 th turn was calculated to be 85.4%. It can be seen that the Fe-PB-W-IPA has a low capacity although it has a good cycle stability.
Example 6
Dispersing 200 mg of Fe-PB prepared in example 1 in 100 ml of deionized water under the protection of nitrogen atmosphere, adding 2 ml of isopropanol dispersant, magnetically stirring for 3 hours, performing suction filtration and washing, and performing vacuum filtration and washing at 80 DEG o Drying in an oven C for 12h to obtain Fe-PB-W-IPA-N 2 . Mixing Fe-PB-W-IPA-N 2 The positive electrode material, acetylene black and polyvinylidene fluoride (PVDF) are stirred into slurry, the slurry is coated on an aluminum foil, and a positive electrode material pole piece is manufactured through drying, membrane punching and membrane pressing. 1M NaClO containing 2 wt.% FEC and taking metallic sodium as a counter electrode and Grade GF/D as a diaphragm 4 And (EC + DMC + EMC) (EC: DMC: EMC =1:1:1) is a battery assembled by the electrolyte, and the voltage range is 2.0-4.2V. FIG. 2 shows Fe-PB-W-IPA-N 2 XRD of (a) versus standard card. Apparently, Fe-PB-W-IPA-N 2 Shows good crystallinity, and the diffraction peaks thereof are basically consistent with those of standard cards (JCPDS, number 52-1907) but are at 24.16, 38.54 and 49.46 o The peak separation phenomenon also appears at the position, which shows that Fe-PB-W-IPA-N 2 Is monoclinic phase. FIG. 8 shows Fe-PB-W-IPA-N 2 The cathode material is 100 mA g -1 The charge/discharge curves of the 1 st, 5 th and 50 th circles at the current density of (1), and FIG. 9 is a graph of Fe-PB-W-IPA-N 2 The cathode material is 100 mA g -1 Current density of (a). Fe-PB-W-IPA-N 2 The first discharge capacity of the discharge electrode reaches 159.1 mAh g -1 Capacity after 5 and 50 cycles of 109.7 mAh g -1 And 96.6 mAh g -1 (ii) a Taking into account the activation of the electrodes, the first one is calculatedThe capacity retention ratio of 50 cycles to 5 cycles was 88.1%. It can be seen that Fe-PB-W-IPA-N 2 The cycling stability of the catalyst is better, and the capacity of the catalyst is higher.
In fact, when Fe-PB prepared in example 1 is dispersed in 100 ml of deionized water under the protection of nitrogen atmosphere and 0.1, 0.5, 1, 3, 5, 10 ml of isopropanol dispersant is added, the obtained product has a first discharge capacity of 140.6 mAh g -1 、143.5 mAh g -1 、148.7 mAh g -1 、155.6 mAh g -1 、152.2 mAh g -1 And 145.3 mAh g -1 The capacity after 50 cycles of circulation is 100.2 mAh g -1 、102.3 mAh g -1 、114.2 mAh g -1 、126.1 mAh g -1 、124.7 mAh g -1 、108.5 mAh g -1 。
When Fe-PB prepared in example 1 is dispersed in 100 ml of deionized water under the protection of nitrogen atmosphere and 2 ml of isoamyl alcohol dispersant is added, the initial discharge capacity of the obtained product reaches 156.0 mAh g -1 The capacity after 50 cycles of circulation is 95.9 mAh g -1 。
Aiming at the test, the same operation steps of using ethylene glycol as a dispersing agent are carried out, and the obtained product has the first discharge capacity of 150.7 mAh g -1 And the capacity is 105.2 mAh g after 50 cycles of circulation -1 。
Surprisingly, when 2 ml of methanol was added as a dispersant, the effect was disappointing and the product obtained had a first discharge capacity of 145.8 mAh g -1 And the capacity is 92.3 mAh g after 50 cycles of circulation -1 。
In order to optimize the solvent type, the present application also carried out tests with tetrahydrofuran as dispersant, and likewise, when 2 ml of this dispersant was added, the first discharge capacity of the product was as high as 156.3 mAh g -1 And the capacity is 80.9 mAh g after 50 cycles of circulation -1 This result is not satisfactory.
The Applicant has also carried out tests with acetone as dispersant, i.e. when 2 ml of acetone are added as dispersant, the product obtained has a first discharge capacity of up to 120 mAh g -1 The capacity after 50 cycles of circulation is 89.6 mAh g -1 The results are still unsatisfactory.
Claims (8)
1. The preparation method of the long-life iron-based Prussian blue anode material is characterized by comprising the following steps of:
(1) dissolving Fe salt and sodium citrate in deionized water to prepare a solution A, dissolving a proper amount of sodium ferrocyanide and an antioxidant ascorbic acid in a proper amount of deionized water to prepare a solution B, and dissolving a dispersant polyvinylpyrrolidone and a proper amount of a sodium supplement agent in deionized water to prepare a solution C;
(2) in N 2 Under the conditions of atmosphere, heating and stirring, simultaneously dripping the solution A and the solution B into the solution C for reaction to obtain a white suspension, continuing to heat and stir the white suspension uniformly, aging at room temperature, centrifugally washing the white precipitate obtained after aging for a plurality of times, and then drying in vacuum at the temperature of 100-140 ℃ to obtain an initial iron-based Prussian blue compound;
(3) and dispersing a certain amount of initial iron-based Prussian blue compounds in deionized water under the protection of inert atmosphere, adding a small amount of alcohol dispersant, magnetically stirring for a certain time, performing suction filtration, washing and drying to obtain the modified iron-based Prussian blue sodium ion battery cathode material.
2. The method for preparing the long-life iron-based prussian blue cathode material as claimed in claim 1, wherein the salt of Fe in step (1) is ferrous chloride or ferrous acetate; the molar ratio of the Fe salt to the sodium citrate is 1: 1-10, and preferably the molar ratio of the Fe-containing salt to the sodium citrate is 1: 5.
3. The method for preparing a long-life iron-based prussian blue positive electrode material as claimed in claim 1, wherein the molar ratio of sodium ferrocyanide, Fe salt and ascorbic acid in step (1) is 1: 0.6-1.5: 3 to 10.
4. The method for preparing the long-life iron-based Prussian blue cathode material as claimed in claim 1, wherein the sodium supplement agent in step (1) is sodium chloride (NaCl) or sodium carbonate (Na) 2 CO 3 Sodium acetate CH 3 At least one of COONa, polyvinylpyrrolidone and sodium supplement agent in a mass ratio of 1-1.5: 5.5-7.
5. The method for preparing a long-life iron-based prussian blue positive electrode material as claimed in claim 1, wherein in step (2), N is 2 Under the atmosphere, the stirring speed is 400-600 rpm, the reaction temperature is 45-55 ℃, and the dropping speed of the solution A and the solution B is controlled at 8-10 ml/h.
6. The preparation method of the long-life iron-based Prussian blue cathode material as claimed in claim 1, wherein in the step (2), the heating and stirring time is 10-12h at 45-55 ℃; aging for 10-30h at room temperature; 100-140 o And C, vacuum drying for 10-12 h.
7. The method for preparing the long-life iron-based prussian blue cathode material as claimed in claim 1, wherein the inert atmosphere in step (3) is argon or nitrogen.
8. The preparation method of the long-life iron-based Prussian blue cathode material as claimed in claim 1, wherein the alcohol dispersant in the step (3) is one or more of ethanol, ethylene glycol, isopropanol, isobutanol, n-butanol, isoamyl alcohol and cyclohexanol; the adding amount is 0.1-10% of the mass of the initial iron-based Prussian blue compound; adding an alcohol dispersant, stirring for 1-6 h, and performing suction filtration and washing.
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| CN117509675B (en) * | 2023-11-08 | 2024-04-30 | 武汉中科先进材料科技有限公司 | Iron-based Prussian blue with low crystal water content, and preparation method and application thereof |
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