CN114256459A - Fluoro-mixed ferric manganese sodium pyrophosphate binary positive electrode material, preparation method and application thereof in sodium ion battery - Google Patents
Fluoro-mixed ferric manganese sodium pyrophosphate binary positive electrode material, preparation method and application thereof in sodium ion battery Download PDFInfo
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- UMZUVDAJYPZSCI-UHFFFAOYSA-K sodium [hydroxy(oxido)phosphoryl] phosphate manganese(2+) Chemical compound [O-]P([O-])(=O)OP(=O)([O-])O.[Mn+2].[Na+] UMZUVDAJYPZSCI-UHFFFAOYSA-K 0.000 title claims abstract description 57
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 80
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 39
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 37
- 239000010405 anode material Substances 0.000 claims abstract description 31
- 239000011572 manganese Substances 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 229920000447 polyanionic polymer Polymers 0.000 claims abstract description 24
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 21
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical class [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 59
- 229910002804 graphite Inorganic materials 0.000 claims description 41
- 239000010439 graphite Substances 0.000 claims description 41
- 238000003756 stirring Methods 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 15
- 239000011737 fluorine Substances 0.000 claims description 13
- 229910052731 fluorine Inorganic materials 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 239000005457 ice water Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 239000012286 potassium permanganate Substances 0.000 claims description 8
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical group [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 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 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 5
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 5
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 4
- 229940040526 anhydrous sodium acetate Drugs 0.000 claims description 4
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 4
- ALIMWUQMDCBYFM-UHFFFAOYSA-N manganese(2+);dinitrate;tetrahydrate Chemical group O.O.O.O.[Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ALIMWUQMDCBYFM-UHFFFAOYSA-N 0.000 claims description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 235000013024 sodium fluoride Nutrition 0.000 claims description 4
- 239000011775 sodium fluoride 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
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 239000006183 anode active material Substances 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical class [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 239000006258 conductive agent Substances 0.000 claims description 2
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 claims description 2
- 235000019850 ferrous citrate Nutrition 0.000 claims description 2
- 239000011640 ferrous citrate Substances 0.000 claims description 2
- APVZWAOKZPNDNR-UHFFFAOYSA-L iron(ii) citrate Chemical compound [Fe+2].OC(=O)CC(O)(C([O-])=O)CC([O-])=O APVZWAOKZPNDNR-UHFFFAOYSA-L 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 30
- 239000010406 cathode material Substances 0.000 abstract description 7
- 230000009471 action Effects 0.000 abstract description 4
- 230000001351 cycling effect Effects 0.000 abstract description 4
- 238000007599 discharging Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 5
- -1 fluorine ions Chemical class 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000002243 precursor Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229960004543 anhydrous citric acid Drugs 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- DMOXNIKYXJYCFQ-UHFFFAOYSA-N (2-hydroxy-1-phosphonooxyethyl) dihydrogen phosphate Chemical compound OP(=O)(O)OC(CO)OP(O)(O)=O DMOXNIKYXJYCFQ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000234314 Zingiber Species 0.000 description 1
- UBYFFBZTJYKVKP-UHFFFAOYSA-J [Mn+4].[O-]P([O-])(=O)OP([O-])([O-])=O Chemical compound [Mn+4].[O-]P([O-])(=O)OP([O-])([O-])=O UBYFFBZTJYKVKP-UHFFFAOYSA-J 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 229960004106 citric acid Drugs 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229960001367 tartaric acid Drugs 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
Images
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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/62—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
Abstract
The invention discloses a fluoro-mixed ferric manganese sodium pyrophosphate binary positive electrode material which comprises a fluoro-doped ferric manganese binary mixed polyanion compound and graphene, wherein the graphene is respectively inserted and paved in the interior and on the surface of the fluoro-doped ferric manganese binary mixed polyanion compound. The invention also discloses a preparation method of the modified ferro-manganese binary mixed polyanion compound cathode material. The invention also discloses an application of the fluoro mixed ferric manganese pyrophosphate sodium binary anode material in a sodium ion battery. In the fluoro-mixed ferric manganese sodium pyrophosphate binary anode material, the electronic conductivity of the material is greatly improved under the combined action of the graphene and the fluorine-doped ferric manganese binary mixed polyanion compound, the volume expansion of the material in the charging and discharging processes can be slowed down, the capacity of the material is greatly improved, and the cycling stability of the material is improved.
Description
Technical Field
The invention relates to the field of energy storage material sodium ion battery positive electrode materials, in particular to a fluoro-mixed ferric manganese pyrophosphate sodium binary positive electrode material, a preparation method and application thereof in a sodium ion battery.
Background
The use of traditional fossil energy causes environmental pollution and its reserves are decreasing day by day, in response to the calls of the national "carbon peaking" and "carbon neutralizing" strategies. The development and utilization of clean energy such as wind energy and solar energy are more and more paid attention by people. However, the generation of new energy is easily restricted by climate and environment, and the energy produced by the new energy has the characteristics of intermittency and instability. The energy storage battery can store the clean energy, and then stably output and utilize the energy storage battery, so that the problems of intermittence and instability of the clean energy are well solved.
The Sodium Ion Battery (SIB) as an energy storage battery has the characteristics of abundant resource reserves, low price, high working voltage and the like, and has wide application prospects in the field of large-scale energy storage. However, the iron-manganese-based mixed polyanion phosphate material has the characteristics of low electronic conductivity and the like, and particularly, when the content of manganese is increased, the material can have a higher voltage, but the stability of the material is reduced because the manganese-containing material is generally influenced by the Zingiber Taylor effect. Therefore, how to improve the electronic conductivity of the material and the cycling stability of the material becomes one of the key problems for researching the material.
Disclosure of Invention
The invention aims to solve the problems and provides a fluoro-mixed ferric manganese pyrophosphate sodium binary positive electrode material, a preparation method and application thereof in a sodium ion battery.
The invention provides a fluoro mixed ferric manganese pyrophosphate sodium binary anode material, which has the following characteristics: the fluoro mixed ferric manganese sodium pyrophosphate binary positive electrode material comprises a fluoro doped ferric manganese binary mixed polyanion compound and graphene, wherein the graphene is respectively inserted and paved in the interior and on the surface of the fluoro doped ferric manganese binary mixed polyanion compound.
In the inventionThe fluoro mixed ferric manganese sodium pyrophosphate binary positive electrode material can also have the following characteristics: the chemical equation of the fluoro mixed ferric manganese pyrophosphate sodium binary anode material is as follows: na (Na)4-2xFe3-yMny(PO4)2- xFxP2O7@ C @ rGO, the value range of x is: x is more than or equal to 0.01 and less than or equal to 0.5, and the value range of y is as follows: y is more than or equal to 0.1 and less than or equal to 2.9. Or Na3-2xFe2- yMny(PO4)1-xFxP2O7@ C @ rGO, the value range of x is: x is more than or equal to 0.01 and less than or equal to 0.5, and the value range of y is as follows: y is more than or equal to 0.1 and less than or equal to 1.9. The quality of rGO is as follows: rGO is more than or equal to 1 percent and less than or equal to 5 percent by weight.
The invention provides a preparation method of a fluoro mixed ferric manganese sodium pyrophosphate binary anode material, which is used for preparing the fluoro mixed ferric manganese sodium pyrophosphate binary anode material and has the characteristics that the preparation method comprises the following steps: step 1, dissolving an iron source, a manganese source, a sodium source, a phosphorus source, a fluorine source and a reducing agent in deionized water to obtain a solution A; step 2, dissolving a graphene oxide solution and hexadecyl trimethyl ammonium bromide in deionized water to obtain a solution B; and 3, adding the solution B into the solution A, stirring, drying and calcining to obtain the fluoro mixed ferric manganese sodium pyrophosphate binary anode material.
The preparation method of the fluoro mixed ferric manganese pyrophosphate sodium binary anode material provided by the invention can also have the following characteristics: in the step 1, the molar ratio of the iron source, the manganese source, the sodium source, the phosphorus source, the fluorine source and the reducing agent is as follows: (1 to 2), (1 to 4), (1 to 5), (0.01 to 0.5), (1 to 5).
The preparation method of the fluoro mixed ferric manganese pyrophosphate sodium binary anode material provided by the invention can also have the following characteristics: in the step 1, the phosphorus source is any one of ammonium dihydrogen phosphate and hydroxyethylidene diphosphoric acid, the sodium source is any one of sodium dihydrogen phosphate, sodium nitrate and anhydrous sodium acetate, the fluorine source is sodium fluoride, the manganese source is manganese nitrate tetrahydrate, the iron source is any one of ferric nitrate nonahydrate, ferric oxalate and ferrous citrate, and the reducing agent is any one of citric acid, ascorbic acid and tartaric acid.
The preparation method of the fluoro mixed ferric manganese pyrophosphate sodium binary anode material provided by the invention can also have the following characteristics: in step 2, the preparation method of the graphene oxide solution is as follows: step 2-1, putting the flake graphite into a mixed solution of a concentrated sulfuric acid solution and a concentrated nitric acid solution, standing, washing and filtering with deionized water, fully washing and drying to obtain intercalated graphite; step 2-2, heating the tube furnace to 1050 ℃, placing the intercalated graphite in a magnetic boat, and feeding the magnetic boat into the tube furnace to expand until the volume of black solids in the magnetic boat is not expanded any more, so as to obtain thermal expansion graphite; step 2-3, respectively adding thermal expansion graphite, potassium persulfate, phosphorus pentoxide and concentrated sulfuric acid solution into a three-neck flask, uniformly stirring, slowly heating to 80 ℃, preserving heat for 5 hours, cooling to room temperature, slowly pouring an ice water mixture, stirring until heat release is complete, filtering, fully washing with deionized water, and drying to obtain pre-oxidized graphite; step 2-4, mixing pre-oxidized graphite and concentrated sulfuric acid solution, adding potassium permanganate for reaction, adding hydrogen peroxide, centrifuging and collecting precipitate; step 2-5, washing the precipitate for several times by using dilute hydrochloric acid until no sulfate ions exist in the solution, washing the precipitate by using deionized water until the solution is neutral, and collecting and drying graphite oxide at the bottom for later use; and 2-6, weighing the dried graphite oxide, adding the graphite oxide into deionized water, and stirring and ultrasonically stripping to obtain a graphene oxide solution with uniform color.
The preparation method of the fluoro mixed ferric manganese pyrophosphate sodium binary anode material provided by the invention can also have the following characteristics: in the step 2-1, the scale graphite is 32 meshes, the volume ratio of the concentrated sulfuric acid solution to the concentrated nitric acid solution is 3:1, in the step 2-2, the expansion time in the tube furnace is 10s, and in the step 2-3, the volume ratio of the thermally expanded graphite, the potassium persulfate, the phosphorus pentoxide and the concentrated sulfuric acid solution is 3 g: 3 g: 3 g: 250ml, and in the step 2-4, the proportion of the pre-oxidized graphite to the concentrated sulfuric acid solution is 3 g: 250ml, in step 2-5, the concentration of dilute hydrochloric acid is 10%, the method for detecting whether sulfate ions exist in the solution is to detect by using a saturated barium chloride solution, and in step 2-6, the ratio of graphite oxide to deionized water is 0.1 g: 1L of the compound.
The preparation method of the fluoro mixed ferric manganese pyrophosphate sodium binary anode material provided by the invention can also have the following characteristics: the specific operation process of the step 2-4 is as follows: respectively adding pre-oxidized graphite and concentrated sulfuric acid solution into a three-neck flask, uniformly stirring at room temperature, placing in an ice water bath, slowly adding 15g of potassium permanganate into the three-neck flask, removing the ice water bath after the potassium permanganate is completely added, stirring at room temperature for 1h, slowly heating to 35 ℃, reacting for 2h, pouring reaction liquid into a large amount of ice water mixture after the reaction is finished, stirring until the solution completely releases heat, adding 40ml of hydrogen peroxide, centrifuging, and collecting precipitate.
The invention provides an application of a fluoro-mixed ferric manganese pyrophosphate sodium binary anode material in a sodium ion battery, which is characterized in that: the fluoro-mixed ferric manganese sodium pyrophosphate binary anode material is used as an anode active material of a sodium ion battery to obtain a sodium ion battery anode, wherein the fluoro-mixed ferric manganese sodium pyrophosphate binary anode material is the fluoro-mixed ferric manganese sodium pyrophosphate binary anode material provided by the invention.
The fluoro mixed ferric manganese pyrophosphate sodium binary positive electrode material provided by the invention can be applied to a sodium ion battery, and has the following characteristics: the preparation method for obtaining the positive electrode of the sodium-ion battery comprises the following steps: and mixing the modified ferro-manganese binary mixed polyanion compound, a binder and a conductive agent to prepare slurry, coating the slurry on a current collector, and curing to obtain the positive electrode of the sodium-ion battery.
Action and Effect of the invention
According to the fluoro mixed ferric manganese sodium pyrophosphate binary positive electrode material, the preparation method and the application thereof in the sodium ion battery, the fluoro mixed ferric manganese sodium pyrophosphate binary positive electrode material comprises the fluoro doped ferric manganese binary mixed polyanion compound and the graphene, and the graphene respectively penetrates and lays in the interior and on the surface of the fluoro doped ferric manganese binary mixed polyanion compound. Graphene is crisscrossed among the materials or attached to the surface of the materials, and meanwhile fluorine ion doping with strong electronegativity can affect the outer electronic structure of the materials. Therefore, the two components have the combined action to greatly improve the electronic conductivity of the material, and simultaneously, the volume expansion of the material in the charge and discharge process can be slowed down, the capacity of the material is improved to a great extent, and the cycling stability of the material is improved.
The preparation method of the fluoro mixed ferric manganese sodium pyrophosphate binary anode material has wide raw material sources and simple operation, and can be used for large-scale production. The modified mixed polyanionic compound cathode material prepared by the method has the characteristics of high electronic conductivity, high reversible discharge capacity, high energy density and the like, and lays a good foundation for further development of sodium-ion batteries.
Drawings
Fig. 1 is an X-ray diffraction pattern (XRD pattern) of the modified fluoro mixed ferric manganese pyrophosphate sodium doped with fluorine ion supported graphene in example 1 of the present invention;
FIG. 2 is an XRD (X-ray diffraction) pattern of a graphene-loaded iron-manganese binary mixed polyanion compound cathode material in a comparative example of the invention;
fig. 3 is a charge-discharge cycle curve diagram of the graphene-loaded iron-manganese binary mixed polyanion compound positive electrode material under a multiplying power of 0.1C in the comparative example of the present invention;
fig. 4 is a charge-discharge cycle curve diagram of the graphene-loaded fluoride ion-doped modified fluoro mixed ferric manganese pyrophosphate sodium binary positive electrode material under a magnification of 0.1C in example 1 of the present invention;
fig. 5 is a scanning electron microscope image of the modified fluoro mixed ferric manganese pyrophosphate sodium binary positive electrode material doped with fluorine ions loaded by graphene in example 1 of the present invention; and
fig. 6 is a cycle chart of the positive electrode material before and after modification by fluorine ion doping in comparative example and example 1 of the present invention at a rate of 10C.
Detailed Description
In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the present invention easy to understand, the following embodiments specifically describe the fluoro-mixed ferric manganese pyrophosphate sodium binary positive electrode material, the preparation method and the application thereof in the sodium ion battery with reference to the accompanying drawings.
< example >
The embodiment provides a preparation method of a fluoro mixed ferric manganese pyrophosphate sodium binary anode material.
The preparation method of the fluoro mixed ferric manganese pyrophosphate sodium binary anode material in the embodiment comprises the following steps:
step S1, dissolving 3.03g of ferric nitrate nonahydrate, 1.8826g of manganese nitrate tetrahydrate, 2.2833g of ammonium dihydrogen phosphate, 0.0063g of sodium fluoride, 1.6035g of anhydrous sodium acetate and 4.3227g of anhydrous citric acid in 100mL of deionized water in a beaker, and stirring for 1h to obtain a solution A.
Step S2, dispersing 18.8mL of Graphene Oxide (GO) solution with the concentration of 3.33mg/mL and 0.3g of hexadecyl trimethyl ammonium bromide into 30mL of deionized water, and carrying out ultrasonic treatment for 1h to obtain a solution B.
The preparation method of the GO solution comprises the following steps:
step S2-1, putting the flake graphite into a mixed solution of a concentrated sulfuric acid solution and a concentrated nitric acid solution, standing for about 12 hours, washing and filtering with deionized water, fully washing, and drying at 120 ℃ for about 12 hours to obtain intercalated graphite;
step S2-2, heating the tube furnace to 1050 ℃, placing the intercalated graphite in a magnetic boat, and feeding the magnetic boat into the tube furnace to expand until the volume of black solid in the magnetic boat is not expanded any more, so as to obtain thermal expansion graphite;
step S2-3, respectively adding 3g of thermal expansion graphite, 3g of potassium persulfate, 3g of phosphorus pentoxide and 250ml of concentrated sulfuric acid into a three-neck flask, stirring uniformly, slowly heating to 80 ℃, keeping the temperature for 5 hours, cooling to room temperature, slowly pouring an ice water mixture, stirring until heat release is complete, filtering, fully washing with deionized water, and drying at 120 ℃ for 12 hours to obtain pre-oxidized graphite;
and step S2-4, respectively adding 3g of pre-oxidized graphite and 250ml of concentrated sulfuric acid into a three-neck flask, uniformly stirring at room temperature, placing the three-neck flask into an ice water bath, slowly adding 15g of potassium permanganate into the three-neck flask, removing the ice water bath after the potassium permanganate is completely added, stirring at room temperature for 1h, slowly heating to 35 ℃, reacting for 2h, pouring the reaction solution into a large amount of ice water mixture after the reaction is finished, stirring until the solution completely releases heat, adding 40ml of hydrogen peroxide, centrifuging, collecting and precipitating.
Step S2-5, washing the precipitate for several times by using 10% diluted hydrochloric acid until no sulfate ions exist in the solution, washing the precipitate by using deionized water until the solution is neutral, and collecting bottom graphite oxide for later use after drying;
and step S2-6, weighing 0.1g of the graphite oxide obtained after drying, adding the graphite oxide into 1L of deionized water, and stirring and ultrasonically stripping to obtain a GO solution with uniform color.
And step S3, mixing the solution A and the solution B, and stirring for 2h to obtain a precursor solution. The precursor solution is dried by distillation under the condition of 80 ℃ oil bath, and then dried for 8h under vacuum at 90 ℃. And heating the dried raw materials to 550 ℃ at the heating rate of 2 ℃/min in the atmosphere of 5% hydrogen and 95% argon, calcining, and preserving heat for 10 hours to obtain the fluorine-doped Na3.94Fe1.5Mn1.5(PO4)1.97F0.03P2O7@ C @ rGO positive electrode material.
Fig. 1 is an X-ray diffraction diagram of the modified fluoro mixed ferric manganese pyrophosphate binary positive electrode material doped with fluorine ions loaded by graphene in this example.
As shown in fig. 1, it can be seen that the fluorine doping and graphene loading did not change the crystal structure of the material, which was phase pure.
< comparative example >
The comparative example provides a preparation method of a graphene loaded iron-manganese binary mixed polyanion compound cathode material.
The preparation method of the graphene-loaded iron-manganese binary mixed polyanion compound positive electrode material in the embodiment is similar to that in embodiment 1, except that:
step S1, dissolving 3.03g of ferric nitrate nonahydrate, 1.8826g of manganese nitrate tetrahydrate, 2.3006g of ammonium dihydrogen phosphate, 1.6404g of anhydrous sodium acetate and 4.3227g of anhydrous citric acid in 50mL of deionized water in a beaker, and stirring for 1h to obtain a precursor solution.
The remaining steps were the same as in example 1.
Fig. 2 is an X-ray diffraction pattern of the graphene-loaded ferrimanganic binary mixed polyanion positive electrode material in the comparative example.
As can be seen from FIG. 2, the Na prepared in the comparative example was found after comparison with the 89-0579PDF standard card4Fe1.5Mn1.5(PO4)2P2O7@ C @ rGO is a pure phase.
In this example, a charge-discharge cycle test of the fluoro mixed ferric manganese sodium pyrophosphate binary cathode material obtained in the comparative example and the example 1 at a rate of 0.1C is also provided.
Fig. 3 is a charge-discharge cycle curve diagram of the graphene-loaded iron-manganese binary mixed polyanion compound positive electrode material in the comparative example at a magnification of 0.1C.
Fig. 4 is a charge-discharge cycle curve diagram of the graphene-supported fluoride ion doped modified fluoro mixed ferric manganese pyrophosphate sodium binary positive electrode material in example 1 at a magnification of 0.1C.
As can be seen from fig. 3 and 4, the discharge capacity of the graphene-loaded fluoride ion-doped modified fluoro-mixed ferric manganese sodium pyrophosphate binary positive electrode material prepared in example 1 at 0.1C is far better than that of the graphene-loaded ferric manganese binary mixed polyanion compound positive electrode material in the comparative example (before modification), which indicates that fluorine doping plays a positive role in increasing the material capacity, and the discharge capacity comparison of the graphene-loaded fluoride-doped ferric manganese binary mixed polyanion positive electrode material at 0.1C shows that the discharge capacity of the graphene-loaded fluoride-doped ferric manganese binary mixed polyanion positive electrode material reaches 121.9mAh g-1Approaching the theoretical capacity.
Fig. 5 is a scanning electron microscope image of the modified fluoro mixed ferric manganese pyrophosphate sodium binary cathode material doped with fluorine ions loaded by graphene in example 1.
As can be seen from FIG. 5, aggregation of the material in the synthesis process can be inhibited to a certain extent by graphene loading, and the particle size of the material is 100-500 nm.
Fig. 6 is a cycle chart of the positive electrode material before and after modification by fluorine ion doping in comparative example and example 1 at a rate of 10C.
As shown in fig. 6, the cycle performance of the modified material doped with fluorine ions is greatly improved compared with that before modification.
Effects and effects of the embodiments
According to the fluoro mixed ferric manganese sodium pyrophosphate binary positive electrode material, the preparation method and the application thereof in the sodium ion battery, the fluoro mixed ferric manganese sodium pyrophosphate binary positive electrode material comprises the fluoro doped ferric manganese binary mixed polyanion compound and the graphene, and the graphene respectively penetrates and spreads in the interior and on the surface of the fluoro doped ferric manganese binary mixed polyanion compound. Graphene is crisscrossed among the materials or attached to the surface of the materials, and meanwhile fluorine ion doping with strong electronegativity can affect the outer electronic structure of the materials. Therefore, the two components have the combined action to greatly improve the electronic conductivity of the material, and simultaneously, the volume expansion of the material in the charge and discharge process can be slowed down, the capacity of the material is improved to a great extent, and the cycling stability of the material is improved.
The preparation method of the fluoro mixed ferric manganese sodium pyrophosphate binary anode material related to the embodiment has the advantages of wide raw material source, simple operation and large-scale production. The modified mixed polyanionic compound cathode material prepared by the method has the characteristics of high electronic conductivity, high reversible discharge capacity, high energy density and the like, and lays a good foundation for further development of sodium-ion batteries.
The above embodiments are preferred examples of the present invention, and are not intended to limit the scope of the present invention.
Claims (10)
1. A fluoro-mixed ferric manganese sodium pyrophosphate binary anode material is characterized in that:
the fluoro-mixed ferric manganese pyrophosphate sodium binary anode material comprises a fluoro-doped ferric manganese binary mixed polyanion compound and graphene,
the graphene is respectively inserted into and paved on the interior and the surface of the fluorine-doped iron-manganese binary mixed polyanion compound.
2. The fluoro-mixed ferric manganese sodium pyrophosphate binary positive electrode material according to claim 1, characterized in that:
the chemical equation of the fluoro mixed ferric manganese pyrophosphate sodium binary anode material is as follows:
Na4-2xFe3-yMny(PO4)2-xFxP2O7@C@rGO，
the value range of x is as follows: x is more than or equal to 0.01 and less than or equal to 0.5, and the value range of y is as follows: y is more than or equal to 0.1 and less than or equal to 2.9,
or
Na3-2xFe2-yMny(PO4)1-xFxP2O7@C@rGO，
The value range of x is as follows: x is more than or equal to 0.01 and less than or equal to 0.5, and the value range of y is as follows: y is more than or equal to 0.1 and less than or equal to 1.9,
the quality of rGO is as follows: rGO is more than or equal to 1 percent and less than or equal to 5 percent by weight.
3. A preparation method of a fluoro-mixed ferric manganese sodium pyrophosphate binary positive electrode material is used for preparing the fluoro-mixed ferric manganese sodium pyrophosphate binary positive electrode material as claimed in any one of claims 1-2, and is characterized by comprising the following steps:
step 1, dissolving an iron source, a manganese source, a sodium source, a phosphorus source, a fluorine source and a reducing agent in deionized water to obtain a solution A;
step 2, dissolving a graphene oxide solution and hexadecyl trimethyl ammonium bromide in deionized water to obtain a solution B;
and 3, adding the solution B into the solution A, stirring, drying and calcining to obtain the fluoro mixed ferric manganese sodium pyrophosphate binary anode material.
4. The preparation method of the fluoro-mixed ferric manganese pyrophosphate sodium binary anode material as claimed in claim 3, characterized in that:
in step 1, the molar ratio of the iron source, the manganese source, the sodium source, the phosphorus source, the fluorine source and the reducing agent is as follows: (1 to 2), (1 to 4), (1 to 5), (0.01 to 0.5), (1 to 5).
5. The preparation method of the fluoro-mixed ferric manganese pyrophosphate sodium binary anode material as claimed in claim 3, characterized in that:
wherein in the step 1, the phosphorus source is any one of ammonium dihydrogen phosphate and hydroxyl ethylidene diphosphonic acid,
the sodium source is any one of sodium dihydrogen phosphate, sodium nitrate and anhydrous sodium acetate,
the fluorine source is sodium fluoride and the fluorine source is sodium fluoride,
the manganese source is manganese nitrate tetrahydrate,
the iron source is any one of ferric nitrate nonahydrate, ferric oxalate and ferrous citrate,
the reducing agent is any one of citric acid, ascorbic acid and tartaric acid.
6. The preparation method of the fluoro-mixed ferric manganese pyrophosphate sodium binary anode material as claimed in claim 3, characterized in that:
in step 2, the preparation method of the graphene oxide solution is as follows:
step 2-1, putting the flake graphite into a mixed solution of a concentrated sulfuric acid solution and a concentrated nitric acid solution, standing, washing and filtering with deionized water, fully washing and drying to obtain intercalated graphite;
step 2-2, heating the tube furnace to 1050 ℃, placing the intercalated graphite in a magnetic boat, and feeding the intercalated graphite into the tube furnace to expand until the volume of black solids in the magnetic boat is not expanded any more, so as to obtain thermal expansion graphite;
step 2-3, respectively adding thermal expansion graphite, potassium persulfate, phosphorus pentoxide and concentrated sulfuric acid solution into a three-neck flask, uniformly stirring, slowly heating to 80 ℃, preserving heat for 5 hours, cooling to room temperature, slowly pouring an ice water mixture, stirring until heat release is complete, filtering, fully washing with deionized water, and drying to obtain pre-oxidized graphite;
step 2-4, mixing the pre-oxidized graphite and a concentrated sulfuric acid solution, adding potassium permanganate for reaction, adding hydrogen peroxide, and centrifuging to collect precipitate;
step 2-5, washing the precipitate for several times by using dilute hydrochloric acid until no sulfate ions exist in the solution, washing the precipitate by using deionized water until the solution is neutral, and collecting bottom graphite oxide for later use after drying;
and 2-6, weighing the dried graphite oxide, adding the graphite oxide into deionized water, and stirring and ultrasonically stripping to obtain a graphene oxide solution with uniform color.
7. The preparation method of the fluoro-mixed ferric manganese pyrophosphate sodium binary anode material as claimed in claim 6, characterized in that:
wherein in the step 2-1, the scale graphite is 32 meshes in size, the volume ratio of the concentrated sulfuric acid solution to the concentrated nitric acid solution is 3:1,
in the step 2-2, the time for expansion in the tube furnace is 10s,
in step 2-3, the volume ratio of the thermally expandable graphite, the potassium persulfate, the phosphorus pentoxide, and the concentrated sulfuric acid solution is 3 g: 3 g: 3 g: the volume of the mixture is 250ml,
in the step 2-4, the ratio of the pre-oxidized graphite to the concentrated sulfuric acid solution is 3 g: the volume of the mixture is 250ml,
in the steps 2-5, the concentration of the dilute hydrochloric acid is 10%, the method for detecting whether sulfate ions exist in the solution is to detect by using a saturated barium chloride solution,
in steps 2-6, the ratio of the graphite oxide to the deionized water is 0.1 g: 1L of the compound.
8. The preparation method of the fluoro-mixed ferric manganese pyrophosphate sodium binary anode material as claimed in claim 6, characterized in that:
the specific operation process of the step 2-4 is as follows:
respectively adding the pre-oxidized graphite and concentrated sulfuric acid solution into a three-neck flask, uniformly stirring at room temperature, placing in an ice water bath, slowly adding 15g of potassium permanganate into the three-neck flask, removing the ice water bath after the potassium permanganate is completely added, stirring at room temperature for 1h, slowly heating to 35 ℃, reacting for 2h, pouring the reaction solution into a large amount of ice water mixture after the reaction is finished, stirring until the solution completely releases heat, adding 40ml of hydrogen peroxide, centrifuging, and collecting precipitate.
9. The application of the fluoro-mixed ferric manganese pyrophosphate sodium binary anode material in the sodium ion battery is characterized in that:
the fluoro-mixed ferric manganese sodium pyrophosphate binary anode material is used as an anode active material of a sodium ion battery to obtain a sodium ion battery anode,
the fluoro mixed ferric manganese sodium pyrophosphate binary positive electrode material is the fluoro mixed ferric manganese sodium pyrophosphate binary positive electrode material as set forth in any one of claims 1 to 8.
10. The use of the fluoro-mixed ferric manganese pyrophosphate sodium binary positive electrode material as claimed in claim 9 in a sodium ion battery, characterized in that:
the preparation method of the sodium-ion battery positive electrode comprises the following steps:
and mixing the modified ferro-manganese binary mixed polyanion compound, a binder and a conductive agent to prepare slurry, coating the slurry on a current collector, and curing to obtain the positive electrode of the sodium-ion battery.
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