CN115064695A - Full-iron-based sodium ion battery and preparation method thereof - Google Patents
Full-iron-based sodium ion battery and preparation method thereof Download PDFInfo
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- CN115064695A CN115064695A CN202210831253.8A CN202210831253A CN115064695A CN 115064695 A CN115064695 A CN 115064695A CN 202210831253 A CN202210831253 A CN 202210831253A CN 115064695 A CN115064695 A CN 115064695A
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 174
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 82
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000007773 negative electrode material Substances 0.000 claims abstract description 38
- 239000007774 positive electrode material Substances 0.000 claims abstract description 35
- 239000010405 anode material Substances 0.000 claims abstract description 23
- 239000010406 cathode material Substances 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 15
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 6
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 claims abstract description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000010452 phosphate Substances 0.000 claims abstract description 5
- XWQGIDJIEPIQBD-UHFFFAOYSA-J sodium;iron(3+);phosphonato phosphate Chemical compound [Na+].[Fe+3].[O-]P([O-])(=O)OP([O-])([O-])=O XWQGIDJIEPIQBD-UHFFFAOYSA-J 0.000 claims abstract description 4
- 239000011734 sodium Substances 0.000 claims description 51
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 19
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 16
- 229910052708 sodium Inorganic materials 0.000 claims description 16
- -1 sodium iron pyrophosphate phosphate Chemical compound 0.000 claims description 16
- 239000003792 electrolyte Substances 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 239000012300 argon atmosphere Substances 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910021389 graphene Inorganic materials 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 238000001694 spray drying Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 239000006258 conductive agent Substances 0.000 claims description 6
- 239000011888 foil Substances 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 4
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 4
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 229940040526 anhydrous sodium acetate Drugs 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- 235000019851 ferric sodium diphosphate Nutrition 0.000 claims description 2
- 239000011645 ferric sodium diphosphate Substances 0.000 claims description 2
- 150000001449 anionic compounds Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 7
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 abstract description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract description 2
- VAKIVKMUBMZANL-UHFFFAOYSA-N iron phosphide Chemical compound P.[Fe].[Fe].[Fe] VAKIVKMUBMZANL-UHFFFAOYSA-N 0.000 abstract 1
- 229960004106 citric acid Drugs 0.000 description 10
- 239000003575 carbonaceous material Substances 0.000 description 5
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229960002303 citric acid monohydrate Drugs 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 235000021317 phosphate Nutrition 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 description 4
- 229940048086 sodium pyrophosphate Drugs 0.000 description 4
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 4
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 2
- 150000003949 imides Chemical class 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 229910020626 Na3Fe2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000007144 ferric diphosphate Nutrition 0.000 description 1
- 239000011706 ferric diphosphate Substances 0.000 description 1
- CADNYOZXMIKYPR-UHFFFAOYSA-B ferric pyrophosphate Chemical compound [Fe+3].[Fe+3].[Fe+3].[Fe+3].[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O.[O-]P([O-])(=O)OP([O-])([O-])=O CADNYOZXMIKYPR-UHFFFAOYSA-B 0.000 description 1
- 229940036404 ferric pyrophosphate Drugs 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 229940048084 pyrophosphate Drugs 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- VCCATSJUUVERFU-UHFFFAOYSA-N sodium bis(fluorosulfonyl)azanide Chemical group FS(=O)(=O)N([Na])S(F)(=O)=O VCCATSJUUVERFU-UHFFFAOYSA-N 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
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- 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
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- 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
- H01M10/058—Construction or manufacture
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- 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
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
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- 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
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- 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
- H01M4/5805—Phosphides
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- H01M4/581—Chalcogenides or intercalation compounds thereof
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Abstract
The invention relates to a full-iron-based sodium ion battery and a preparation method thereof, wherein the anode material and the cathode material of the battery are iron-based materials; the anode material takes sodium ferric pyrophosphate phosphate as a raw material, and the cathode material takes one or more of ferric oxide, ferroferric oxide, iron phosphide and ferrous sulfide as a raw material. The positive electrode and the negative electrode of the full-iron-based sodium-ion battery are both made of iron-based materials, the iron-based sodium-ion positive electrode and negative electrode materials have stable frame structures and good thermal stability, the structures are stable in the circulating process, raw materials are cheap and easy to obtain, and the full-iron-based sodium-ion battery has good commercial application potential.
Description
Technical Field
The invention belongs to the technical field of sodium ion batteries, relates to an all-iron-based sodium ion battery, and particularly relates to an all-iron-based sodium ion battery assembled by two iron-based materials and a preparation method thereof.
Background
In the positive electrode material of the sodium ion battery, the iron-based polyanion positive electrode materialThe method has rich resources, an open framework structure and good thermal stability, and is a key technology for constructing the sodium-ion battery with high performance and low cost. In the negative electrode material, materials such as transition metal oxide and transition metal sulfide become Na due to unique morphology and high capacity + Research on storage of negative electrode materials is hot. The iron-based sodium ion positive and negative electrode materials are considered to be battery materials with commercial application prospects due to the characteristics of abundant reserves, easy acquisition, low cost, environmental friendliness and the like on the earth.
For example, chinese patent No. 201911252756.4 discloses an iron-based positive electrode material for sodium ion battery, which includes Na, and a method for preparing the same 3 Fe 2 (SO 4 ) 3 F and intercalation in Na 3 Fe 2 (SO 4 ) 3 A carbon-based material in the F body structure; in the iron-based sodium ion battery positive electrode material, the mass fraction of the carbon-based material is 1-10%. The Na is 3 Fe 2 (SO 4 ) 3 The F anode material can ensure the specific capacity of sodium storage, greatly improves the cycle stability and the rate capability, and has sodium storage electrochemical performance obviously superior to that of a pure-phase NaxFey (SO4) z material; compared with other positive electrode materials containing sodium-containing layered transition metal oxides, polyanionic vanadium-based phosphates and the like, the Na3Fe2(SO4)3F positive electrode material has obvious advantages on working potential and energy density; however, the sintering temperature of the technical scheme is too low, so that the carbon source is not fully carbonized, the self conductivity of the surface carbon coating layer is low, the graphitization degree is poor, and the charge transmission and the sodium ion diffusion are not facilitated.
In addition, chinese patent No. 202111350999.9 discloses a ferric pyrophosphate sodium ion battery
The composite material for positive electrode of cell comprises Na 3.16 Fe 2.42 (P 2 O 7 ) 2 And modified in Na 3.16 Fe 2.42 (P 2 O 7 ) 2 Bulk particle surface and embedded Na 3.16 Fe 2.42 (P 2 O 7 ) 2 A carbon-based material in the bulk particles; the mass fraction of the carbon-based material is 1-10%; adding different kinds of reagentsThe carbon-based material is partially and uniformly coated with Na 3.16 Fe 2.42 (P 2 O 7 ) 2 The other part of the surface of the material particle can be embedded into the body structure, and Na is added 3.16 Fe 2.42 (P 2 O 7 ) 2 The particles are connected in series to play a role of a bridge for charge transfer, and the Na content is obviously improved 3.16 Fe 2.42 (P 2 O 7 ) 2 The conductivity of the anode material body, no harmful waste liquid generated in the synthesis process, low production cost and suitability for large-scale industrial production; however, the technical proposal can enhance Na to a certain extent 3.16 Fe 2.42 (P 2 O 7 ) 2 But the rate capability and structural stability thereof cannot be sufficiently improved.
In view of the above, iron-based sodium ion batteries have room for further development.
Disclosure of Invention
In order to solve the problems of the prior art, the invention provides an all-iron-based sodium-ion battery and a manufacturing method thereof, wherein the positive electrode material and the negative electrode material both have a stable frame structure and good thermal stability, and the raw materials are cheap and easy to obtain.
The invention is realized by the following technical scheme:
the full-iron-based sodium ion battery comprises a positive electrode material, a negative electrode material and electrolyte, and is characterized in that: the positive electrode material and the negative electrode material are both iron-based materials; the positive electrode material is an iron-based mixed anion compound sodium iron pyrophosphate phosphate; the negative electrode material comprises one or more of ferric oxide, ferric phosphide and ferrous sulfide.
The all-iron-based sodium-ion battery is characterized in that: the electrolyte is one or more of sodium perchlorate, sodium hexafluorophosphate, sodium bifluorosulfonylimide and sodium bistrifluoromethylsulfonic acid imide.
The preparation method of the all-iron-based sodium ion battery comprises the steps of preparing an iron-based mixed anion compound anode material, namely sodium iron pyrophosphate phosphate, mixing the anode material, a conductive agent Super P and a binder PVDF according to a mass ratio of 8:1:1, and forming an anode by using a current collector which is an aluminum foil; mixing a negative electrode active material, a conductive agent Super P and a binder P VDF according to a mass ratio of 8:1:1, and forming a negative electrode by using a current collector which is an aluminum foil; and assembling the anode and the cathode with the electrolyte and the Celgard diaphragm in an argon atmosphere with the oxygen partial pressure of less than 0.1ppm to obtain the all-iron-based sodium-ion battery with the anode material and the cathode material both being iron-based materials.
The preparation method of the all-iron-based sodium ion battery comprises the following specific preparation steps:
firstly, preparing a cathode material sodium ferric pyrophosphate phosphate, taking hydrous ferric nitrate as an iron source, hydrous sodium phosphate and anhydrous sodium acetate as sodium sources, citric acid as a carbon source, and desalted water and deionized water as solvents, wherein the molar ratio of Na: fe: the ratio of P is 1.02:0.75:1, the content of C is 1.5-2.5%, the solid content is 30-45%, and then the precursor is obtained by feeding and spray drying at the air inlet rate of 75-85%, the air inlet temperature of 130-; then placing the precursor in argon atmosphere, calcining at the temperature of 500-600 ℃ for 8-15 hours to obtain the anode material Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 ；
Then preparing a negative electrode material or directly selecting a finished iron-based negative electrode material;
assembling the positive electrode material and the negative electrode material into a button cell in a glove box with water oxygen of less than 0.01ppm to obtain the positive electrode material with a chemical formula of Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 The negative electrode is Fe 2 O 3 a/GO all-iron-based sodium ion battery.
The preparation method of the all-iron-based sodium-ion battery comprises the following steps: the preparation method of the negative electrode material comprises the steps of dissolving ferric salt and graphene oxide hydrosol serving as raw materials in 40-70ml of deionized water, uniformly stirring, carrying out ultrasonic dispersion for 50-70min, removing water in a rotary evaporator, collecting, drying again, and collecting iron-based negative electrode material powder.
Has the advantages that:
na proposed by the invention 3 Fe 2 (PO 4 )P 2 O 7 Skillfully adopts the structure of phosphate radical and pyrophosphate radical composite anion, namely stabilizing the productThe structure is characterized in that composite ion doping and composite carbon source coating are simultaneously carried out, so that the ionic conductivity and the electronic conductivity are improved, the capacity is greatly improved, and a high-performance positive electrode material of the sodium battery is provided; the iron-based sodium ion positive and negative electrode materials have stable frame structures and good thermal stability, the structures are stable in the circulating process, the raw materials are cheap and easy to obtain, and the full iron-based sodium ion battery has good commercial application potential.
Compared with the prior art, the technical scheme of the invention has the following beneficial technical effects:
1. the method combines two iron-based sodium ion battery anode and cathode materials into a full iron-based sodium ion full battery, and selects the electrolyte for matching, thereby providing a feasible channel of the sodium ion full battery.
2. In the invention, the anode material and the cathode material are iron-based materials, and because iron is a common element in nature, the iron-based materials are cheap and easy to obtain, so that the cost advantage of the invention is further increased, and the invention has the potential of industrial application.
Drawings
FIG. 1 shows a positive electrode active material Na prepared in example 1 of the present invention 4 Fe 3 (PO 4 ) 2 P 2 O 7 XRD pattern of (a);
FIG. 2 shows Fe, which is an anode active material prepared in example 1 of the present invention 2 O 3 XRD pattern of (a);
fig. 3 is a charge and discharge curve of the iron-based sodium ion full cell prepared in example 1 of the present invention.
Detailed Description
In the following, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The all-iron-based sodium ion battery comprises a positive electrode material, a negative electrode material and electrolyte, wherein the positive electrode and the negative electrode are both iron-based materials. Wherein the content of the first and second substances,
the anode material is iron-based mixed anion compound sodium iron pyrophosphate phosphate;
the cathode material comprises one or more of ferric oxide, ferric phosphide and ferrous sulfide, preferably one or more of ferric oxide, ferroferric oxide, ferric phosphide and ferrous sulfide;
the electrolyte comprises one or more of sodium perchlorate, sodium hexafluorophosphate, sodium bifluorosulfonylimide and sodium bistrifluoromethylsulfonic acid imide.
The preparation method of the all-iron-based sodium ion battery comprises the steps of firstly preparing iron-based mixed anion compound positive electrode material sodium iron pyrophosphate phosphate, mixing the positive electrode material, a conductive agent Super P and an adhesive PVDF according to the mass ratio of 8:1:1, and forming a positive electrode by taking an aluminum foil as a current collector; mixing a negative electrode active material, a conductive agent Super P and a binder P VDF according to a mass ratio of 8:1:1, and forming a negative electrode by using a current collector which is an aluminum foil; assembling the anode and the cathode with electrolyte and a Celgard diaphragm in an argon atmosphere with oxygen partial pressure less than 0.1ppm to obtain the all-iron-based sodium-ion battery with the anode material and the cathode material both being iron-based materials; the preparation method comprises the following specific steps:
firstly, preparing a positive electrode material of ferric sodium pyrophosphate phosphate, taking hydrous ferric nitrate as an iron source, hydrous sodium phosphate and anhydrous sodium acetate as sodium sources, citric acid as a carbon source, and demineralized water and deionized water as solvents, wherein Na: fe: the molar ratio of P is 1-1.04:0.75:1, the content of C is 1.5-2.5%, the solid content is 30-45%, and then the precursor is obtained by feeding and spray drying at 75-85% of air inlet rate, 130-180 ℃ of air inlet temperature and 0.3-0.7% of feeding rate; then placing the precursor in argon atmosphere, calcining at the temperature of 500-600 ℃ for 8-15 hours to obtain the anode material Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 ；
Then preparing a negative electrode material: dissolving ferric salt and graphene oxide hydrosol serving as raw materials in 40-70ml of deionized water, uniformly stirring, performing ultrasonic dispersion for 50-70min, removing water in a rotary evaporator, collecting, drying again, and collecting iron-based negative electrode material powder;
or directly selecting finished iron-based negative electrode material powder;
assembling the positive electrode material and the negative electrode material into a button cell in a glove box with water oxygen of less than 0.01ppm to obtain the positive electrode material with a chemical formula of Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 The negative electrode is Fe 2 O 3 a/GO all-iron-based sodium ion battery.
According to the invention, the iron-based positive electrode and the iron-based negative electrode material are combined into the full iron-based sodium ion battery, the iron-based sodium ion positive electrode and the iron-based negative electrode material have stable frame structures and good thermal stability, the structures are stable in the circulation process, the raw materials are cheap and easy to obtain, and the full iron-based sodium ion battery has good commercial application potential.
The invention is further illustrated by the following specific examples.
Example 1
Preparing a positive electrode material: with Fe (NO) 3 ) 3 ·9H 2 O、NaH 2 PO 4 ·2H 2 O and citric acid are used as raw materials, and deionized water is used as a solvent; wherein, NaH 2 PO 4 ·2H 2 Sodium O source and phosphorus source, Fe (NO) 3 ) 3 ·9H 2 O is an iron source, and citric acid is a carbon source; mixing 6.06gFe (NO) 3 ) 3 ·9H 2 O，3.12g NaH 2 PO 4 ·2H 2 O，0.8gTiO 2 Mixing and adding into 100ml of desalted water, adding 2.10g of citric acid monohydrate, stirring uniformly, and then feeding at 80% of air inlet speed, 180 ℃ of air inlet temperature and 0.5% of feeding speed for spray drying to obtain a precursor; then placing the precursor in argon atmosphere, calcining at 550 ℃ for 10h to obtain the anode material Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 (ii) a The obtained positive electrode active material Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 The XRD pattern of (A) is shown in figure 1;
preparing a negative electrode material: with nanoscale Fe 2 O 3 Taking graphene oxide hydrosol as a raw material, and adding 0.9g of nanoscale Fe 2 O 3 Dissolved in 10ml of graphene oxide hydrosol (11 mg/ml)Stirring in 70ml deionized water, ultrasonically dispersing for 50min, removing water in a rotary evaporator, collecting, oven drying, and collecting Fe as cathode material 2 O 3 GO powder; the prepared negative active material Fe 2 O 3 The XRD pattern of (A) is shown in figure 2;
assembling the prepared anode material and cathode material into a button cell in a glove box with water oxygen lower than 0.01ppm, wherein the electrolyte is sodium perchlorate to obtain the anode material with a chemical formula of Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 The negative electrode is Fe 2 O 3 a/GO all-iron based sodium ion battery.
The charge-discharge curve of the all-iron-based sodium-ion battery prepared in the example 1 is shown in fig. 3, and the performance indexes are as follows: within the voltage range of 2.0-4.3V, the charging specific capacity of 0.2C is 107mAh/g, the reversible specific capacity is 104.8mAh/g, and the first efficiency is 97.9%.
Example 2
Preparing a positive electrode material: with Fe (NO) 3 ) 3 ·9H 2 O、NaH 2 PO 4 ·2H 2 O and citric acid are taken as raw materials, and deionized water is taken as a solvent; wherein, NaH 2 PO 4 ·2H 2 Sodium O source, Fe (NO) 3 ) 3 ·9H 2 O is an iron source, and citric acid is a carbon source; mixing 6.06gFe (NO) 3 ) 3 ·9H 2 O，3.24g NaH 2 PO 4 ·2H 2 O，0.8gTiO 2 Mixing and adding into 100ml of desalted water, adding 2.10g of citric acid monohydrate, stirring uniformly, and then feeding at 75% of air inlet speed, 190 ℃ of air inlet temperature and 0.7% of feeding speed for spray drying to obtain a precursor; then placing the precursor in argon atmosphere, calcining at 500 ℃ for 10h to obtain the anode material Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 ；
The cathode material can directly adopt FeS sold in the market;
assembling the prepared positive electrode material and a commercial FeS negative electrode material into a button cell in a glove box with the water oxygen content lower than 0.01ppm, wherein the electrolyte is sodium bistrifluoromethylenesulfonic acid imide, and obtaining a positive electrode materialChemical formula is Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 And the cathode is an FeS all-iron-based sodium ion battery.
The performance indexes of the all-iron-based sodium-ion battery prepared in the embodiment are as follows: within the voltage range of 2.0-4.3V, the charging specific capacity of 0.2C is 101mAh/g, the reversible specific capacity is 78.2mAh/g, and the first efficiency is 77.4%.
Example 3
Preparing a positive electrode material: with sodium pyrophosphate Na 4 P 2 O 7 ·10H 2 O、FePO 4 Citric acid is used as a raw material; wherein, sodium pyrophosphate Na 4 P 2 O 7 ·10H 2 O is both a sodium source and a phosphorus source, FePO 4 Namely an iron source and a phosphorus source, and citric acid is used as a carbon source; mixing 30.52gNa 4 P 2 O 7 ·10H 2 O、3.44g FePO 4 5.6g of citric acid monohydrate is added into 150mL of water, ball milling is carried out for 3h at the rotating speed of 20rpm, sanding is carried out for 3h at the rotating speed of 2000rpm, and then feeding is carried out at the air inlet speed of 80%, the air inlet temperature of 140 ℃ and the feeding speed of 0.6% for spray drying to obtain a precursor; then placing the precursor in argon atmosphere, calcining for 15h at 600 ℃ to obtain Na 3 Fe 2 (PO 4 )P 2 O 7 ；
Preparing a negative electrode material: with nanoscale Fe 2 O 3 Taking graphene oxide hydrosol as a raw material, and adding 0.9g of nanoscale Fe 2 O 3 Dissolving the powder and 10ml of graphene oxide hydrosol (11 mg/ml) in 50ml of deionized water, stirring uniformly, performing ultrasonic dispersion for 60min, removing water in a rotary evaporator, collecting, drying again, and collecting a negative electrode material Fe 2 O 3 GO powder;
assembling the prepared anode material and cathode material into a button cell in a glove box with water oxygen lower than 0.01ppm, wherein the electrolyte is sodium hexafluorophosphate to obtain the anode material with the chemical formula of Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 The negative electrode is Fe 2 O 3 a/GO all-iron-based sodium ion battery.
The performance indexes of the all-iron-based sodium-ion battery prepared in the embodiment are as follows: within the voltage range of 2.0-4.3V, the charging specific capacity of 0.2C is 103mAh/g, the reversible specific capacity is 100.2mAh/g, and the first efficiency is 97.3%.
Example 4
Preparing a positive electrode material: with sodium pyrophosphate Na 4 P 2 O 7 ·10H 2 O、FePO 4 Citric acid is used as a raw material; wherein, sodium pyrophosphate Na 4 P 2 O 7 ·10H 2 O is both a sodium source and a phosphorus source, FePO 4 Is an iron source, and citric acid is a carbon source; 31.43g of Na 4 P 2 O 7 ·10H 2 O、3.44g FePO 4 5.6g of citric acid monohydrate is added into 150mL of water, ball milling is carried out for 3h at the rotating speed of 20rpm, sanding is carried out for 3h at the rotating speed of 2000rpm, and then feeding is carried out at the air inlet speed of 85%, the air inlet temperature of 130 ℃ and the feeding speed of 0.5% for spray drying to obtain a precursor; then placing the precursor in argon atmosphere, calcining at 600 ℃ for 8h to obtain Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 ；
Preparing a negative electrode material: taking FeP and graphene oxide hydrosol as raw materials, dissolving 0.9g of FeP and 10ml of graphene oxide hydrosol (11 mg/ml) in 40ml of deionized water, stirring uniformly, performing ultrasonic dispersion for 70min, removing water in a rotary evaporator, collecting, drying again, and collecting a negative electrode material FeP/GO powder;
assembling the prepared anode material and cathode material into a button cell in a glove box with water oxygen lower than 0.01ppm, wherein the electrolyte is sodium bis (fluorosulfonyl) imide and sodium bis (trifluoromethanesulfonic) imide to obtain the anode material with a chemical formula of Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 And the cathode is an FeP/GO all-iron-based sodium ion battery.
The performance indexes of the all-iron-based sodium-ion battery prepared in the embodiment are as follows: within the voltage range of 2.0-4.3V, the charging specific capacity of 0.2C is 99.4mAh/g, the reversible specific capacity is 85.3mAh/g, and the first efficiency is 85.8%.
Claims (5)
1. The utility model provides an all-iron-based sodium ion battery, includes cathode material, cathode material and electrolyte, its characterized in that: the positive electrode material and the negative electrode material are both iron-based materials;
the positive electrode material is an iron-based mixed anion compound sodium iron pyrophosphate phosphate;
the negative electrode material comprises one or more of ferric oxide, ferric phosphide and ferrous sulfide.
2. The all-iron based sodium ion battery of claim 1, wherein: the electrolyte is one or more of sodium perchlorate, sodium hexafluorophosphate, sodium bifluorosulfonylimide and sodium bistrifluoromethylsulfonic acid imide.
3. The preparation method of the all-iron-based sodium ion battery according to any one of claims 1 to 2, which comprises the steps of preparing an iron-based mixed anionic compound positive electrode material, namely sodium iron pyrophosphate phosphate, mixing the positive electrode material, a conductive agent Super P and a binder PVDF according to a mass ratio of 8:1:1, and forming a positive electrode by using an aluminum foil as a current collector;
mixing a negative electrode active material, a conductive agent Super P and a binder PVDF according to a mass ratio of 8:1:1, and forming a negative electrode by using a current collector which is an aluminum foil;
and assembling the anode and the cathode with the electrolyte and the Celgard diaphragm in an argon atmosphere with the oxygen partial pressure of less than 0.1ppm to obtain the all-iron-based sodium-ion battery with the anode material and the cathode material both being iron-based materials.
4. The preparation method of the all-iron-based sodium-ion battery according to claim 3, which comprises the following specific steps:
firstly, preparing a positive electrode material of ferric sodium pyrophosphate phosphate, taking hydrous ferric nitrate as an iron source, hydrous sodium phosphate and anhydrous sodium acetate as sodium sources, citric acid as a carbon source, and demineralized water and deionized water as solvents, wherein Na: fe: the molar ratio of P is 1-1.04:0.75:1, the content of C is 1.5-2.5%, the solid content is 30-45%, and then the precursor is obtained by feeding and spray drying at 75-85% of air inlet rate, 130-180 ℃ of air inlet temperature and 0.3-0.7% of feeding rate; then placing the precursor in argon atmosphere, calcining at the temperature of 500-600 ℃ for 8-15 hours to obtain the anode material Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 ；
Then preparing a negative electrode material or directly selecting a finished iron-based negative electrode material;
assembling the above positive electrode material and negative electrode material into button cell in glove box with water oxygen content lower than 0.01ppm to obtain positive electrode material with chemical formula of Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 The negative electrode is Fe 2 O 3 a/GO all-iron-based sodium ion battery.
5. The method of manufacturing an all-iron-based sodium-ion battery according to claim 4, wherein: the preparation method of the negative electrode material comprises the steps of dissolving ferric salt and graphene oxide hydrosol serving as raw materials in 40-70ml of deionized water, uniformly stirring, carrying out ultrasonic dispersion for 50-70min, removing water in a rotary evaporator, collecting, drying again, and collecting iron-based negative electrode material powder.
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| CN116779847A (en) * | 2023-08-11 | 2023-09-19 | 深圳海辰储能控制技术有限公司 | Positive electrode plate, preparation method thereof, energy storage device and power utilization device |
| WO2024011862A1 (en) * | 2022-07-15 | 2024-01-18 | 湖北万润新能源科技股份有限公司 | Iron-based sodium ion full battery and preparation method therefor |
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| CN115064695A (en) * | 2022-07-15 | 2022-09-16 | 湖北万润新能源科技股份有限公司 | Full-iron-based sodium ion battery and preparation method thereof |
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| CN106981636A (en) * | 2017-04-11 | 2017-07-25 | 陕西科技大学 | A kind of preparation method of the nano combined anode material of lithium-ion batteries of FeS/RGO |
| CN109167035A (en) * | 2018-08-22 | 2019-01-08 | 郑州大学 | Carbon-coated ferrous sulfide negative electrode material, preparation method and its sodium-ion battery of preparation |
| CN112510198A (en) * | 2020-12-16 | 2021-03-16 | 武汉大学 | Positive electrode active material, aqueous solution sodium ion battery and electronic device |
| CN113060713A (en) * | 2021-02-25 | 2021-07-02 | 湖北万润新能源科技股份有限公司 | Preparation of Na by homogeneous phase method4Fe3(PO4)2(P2O7) Method and application of |
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| WO2024011862A1 (en) * | 2022-07-15 | 2024-01-18 | 湖北万润新能源科技股份有限公司 | Iron-based sodium ion full battery and preparation method therefor |
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| CN116779847A (en) * | 2023-08-11 | 2023-09-19 | 深圳海辰储能控制技术有限公司 | Positive electrode plate, preparation method thereof, energy storage device and power utilization device |
| CN116779847B (en) * | 2023-08-11 | 2024-01-23 | 深圳海辰储能控制技术有限公司 | Positive electrode plate, preparation method thereof, energy storage device and power utilization device |
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