CN111162256A - Mixed polyanion type sodium ion battery positive electrode material and preparation thereof - Google Patents
Mixed polyanion type sodium ion battery positive electrode material and preparation thereof Download PDFInfo
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- CN111162256A CN111162256A CN201911384103.1A CN201911384103A CN111162256A CN 111162256 A CN111162256 A CN 111162256A CN 201911384103 A CN201911384103 A CN 201911384103A CN 111162256 A CN111162256 A CN 111162256A
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- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 35
- 229920000447 polyanionic polymer Polymers 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000007774 positive electrode material Substances 0.000 title claims description 18
- 239000011734 sodium Substances 0.000 claims abstract description 45
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000002245 particle Substances 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 238000011065 in-situ storage Methods 0.000 claims abstract description 5
- 238000011068 loading method Methods 0.000 claims abstract description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 12
- 239000007921 spray Substances 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 10
- 235000006408 oxalic acid Nutrition 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 229910017677 NH4H2 Inorganic materials 0.000 claims description 7
- 239000010406 cathode material Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims 1
- 239000010405 anode material Substances 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 229910019142 PO4 Inorganic materials 0.000 description 51
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 48
- 239000000463 material Substances 0.000 description 45
- 229910020626 Na3Fe2 Inorganic materials 0.000 description 18
- 239000002131 composite material Substances 0.000 description 10
- 229910000155 iron(II) phosphate Inorganic materials 0.000 description 9
- 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 6
- 239000006258 conductive agent Substances 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000004146 energy storage Methods 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 238000001694 spray drying Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 3
- 235000011180 diphosphates Nutrition 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- -1 Na1-xFeO2 Chemical class 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000527 sonication Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- 229910014485 Na0.44MnO2 Inorganic materials 0.000 description 1
- 229910004589 Na2FeP2O7 Inorganic materials 0.000 description 1
- 229910020657 Na3V2(PO4)3 Inorganic materials 0.000 description 1
- 229910021312 NaFePO4 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000012612 commercial material Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [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 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000012071 phase 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
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
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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
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—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
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- 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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Abstract
The invention relates to a mixed polyanion type sodium ion battery anode material and a preparation method thereof, wherein the anode material is prepared by in-situ loading Na on a graphene layer3Fe2(PO4)(P2O7) And (4) particle composition. Compared with the prior art, the invention has the advantages of good stability of large multiplying power, rich raw material sources, low price, simple and easy synthesis process and the like.
Description
Technical Field
The invention belongs to the technical field of sodium ion batteries, relates to a mixed polyanion type sodium ion battery anode material and preparation thereof, and particularly relates to a novel mixed polyanion type sodium ion battery anode material Na3Fe2(PO4)(P2O7) And Na thereof3Fe2(PO4)(P2O7) Preparation of @ Reduced graphene oxide composite materialA method.
Background
In recent years, in the development of new energy, green renewable clean energy technologies such as water energy, solar energy, wind energy, tidal energy, biological energy and the like have great application value. But the instability and intermittency of the energy supply greatly limit the grid-connected use of the energy supply. Therefore, it is important to develop an efficient energy storage system compatible with new renewable energy. Since the successful commercialization of lithium ion batteries by sony corporation in the nineties of the last century, the applications of lithium ion batteries have expanded rapidly from the first consumer electronics to emerging fields of electric/hybrid vehicles, grid storage, aerospace, and the like. The rapid development of lithium ion secondary batteries as a result of the intense development has also raised the problem of lithium resource shortage. The content of lithium in the crust is about 0.0065%, which is not evenly distributed and difficult to extract. This greatly limits the wide application of lithium ion batteries in the large-scale energy storage field.
The room temperature sodium ion battery is expected to become one of the most competitive batteries for developing large-scale fixed energy storage systems by comprehensively considering two factors of the cost and the storage capacity of the battery. Sodium ion batteries have a similar principle to lithium ion batteries, and it is important that the sodium reserves on earth are much higher than lithium. Currently, typical positive electrode materials for sodium ion batteries are classified into three types, i.e., transition metal oxides, polyanions, and prussian blue analogs, such as Na1-xFeO2，Na0.44MnO2，NaFePO4,Na3V2(PO4)3，Na2FeP2O7，Na4Fe3(PO4)2(P2O7)，Na4Fe[CN]6And the like. The polyanion compound consists of polyanion groups and transition metal elements, and the oxidation-reduction couple of the polyanion couple material has adjustable induction effect, so that people can easily realize the improvement of the potential of the material, thereby obtaining the high-potential anode material. In addition, the polyanion compound has stable structure, is beneficial to realizing long-term circulation, has generally good thermal stability and higher safety, and the advantages ensure that the polyanion compound has higher safetyThe method has great advantages in large-scale fixed energy storage systems.
Chinese patent ZL201610375296.4 discloses a composite positive electrode material for a sodium ion battery and a preparation method thereof, wherein Na grows in situ in a Graphene Oxide (GO) solution by adopting a coprecipitation method2Fe1-xNixP2O7Precursor is calcined to obtain Na2Fe1-xNixP2O7Reducing graphene oxide while preparing nanoparticles to obtain vegetable sponge-like Na2Fe1-xNixP2O7Reduced graphene oxide nanocomposites. The pyrophosphate sodium ion battery has better performance, but the specific energy of the material is lower; a large number of mixed polyanionic materials Na have been reported4Fe3(PO4)2(P2O7) Has higher specific energy and stability, and the specific energy is also greatly improved compared with the pyrophosphate sodium ion battery material.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a mixed polyanion type sodium-ion battery positive electrode material and a preparation method thereof. The specific energy of the prepared material is between pyrophosphate sodium ion battery material and mixed polyanion material Na4Fe3(PO4)2(P2O7) Between materials, and the charge-discharge rate performance ratio of the materials is Na4Fe3(PO4)2(P2O7) The material is a potential power energy storage material with great improvement.
The purpose of the invention can be realized by the following technical scheme:
one of the technical schemes of the invention provides a mixed polyanion type sodium ion battery anode material which is prepared by in-situ loading Na on a graphene layer3Fe2(PO4)(P2O7) And (4) particle composition. Wherein Na3Fe2(PO4)(P2O7) Is the main body of the anode material, due to the electron conductivity of the phosphate anode materialLower, and graphene has better conductivity. Therefore, Na is increased by forming a composite material by loading on the surface of graphene3Fe2(PO4)(P2O7) The electron conductivity of the material.
Graphene as Na3Fe2(PO4)(P2O7) The conductive agent of the material can effectively improve the electronic conductivity of the material. Meanwhile, the increase of the conductive agent can improve the conductivity of the material on one hand, and simultaneously, the increase of the conductive agent can reduce the volume specific energy and the mass specific energy of the whole material. Therefore, the optimal proportion of the conductive agent and the conductive agent in the composite material is realized by optimizing and selecting the proper proportion of the conductive agent through experiments.
Na proposed in this patent3Fe2(PO4)(P2O7) Specific energy of (3) and mixed polyanionic material Na4Fe3(PO4)2(P2O7) The materials are similar. Structurally, in this type of mixed polyanionic material, FeO is the main component6、FeO5、PO4Etc. form a lamellar crystal plane while P2O7Realizing interlayer connection; na proposed in this patent3Fe2(PO4)(P2O7) In the material, there is much P2O7The layered crystal face is connected, and the stability is higher. Thus, experimental studies have found that Na3Fe2(PO4)(P2O7) Material ratio Na4Fe3(PO4)2(P2O7) The material has better high-rate charge-discharge performance.
The second technical scheme of the invention provides a preparation method of a mixed polyanion type sodium ion battery anode material, which comprises the following steps:
(1) weighing Fe (NO)3)3·9H2Dissolving O solid in deionized water, adding oxalic acid, and adding CH3COONa and NH4H2PO4Stirring until the mixture is completely dissolved;
(2) drying the mixed solution obtained in the step (1) to obtain a precursor;
(3) placing the precursor obtained in the step (2) in Ar-H2Calcining under the atmosphere to obtain the target product.
Further, in the step (1), Fe (NO)3)3·9H2O、CH3COONa、NH4H2PO4The addition amount of (A) satisfies: fe3+、Na+And PO4 3+The molar ratio of the three ions was 2:3: 3. Preferably 2:3: 3.
Further, oxalic acid and Fe (NO)3)3·9H2The molar ratio of O is 2.5-3.5: 1.
further, in the step (1), before adding oxalic acid, Fe (NO) is added3)3·9H2And adding the graphene oxide dispersion liquid into the water solution of O.
Further, the concentration of the graphene oxide dispersion liquid is 5g/L, and the graphene oxide dispersion liquid and Fe (NO) are mixed3)3·9H2The addition ratio of O is 50mL-100 mL: 0.02 mol.
Furthermore, after the graphene oxide dispersion liquid is added, ultrasonic dispersion treatment is also carried out.
Further, in the step (2), the drying process comprises: and (3) passing the mixed solution through a spray dryer, wherein the inlet temperature of the spray dryer is set to be 220 ℃, the outlet temperature of the spray dryer is set to be 80 ℃, and the rotating speed of the spray dryer is 400 r/min.
Further, in step (3), Ar-H2In Ar and H2Is 95:5.
Further, in the step (3), the calcining temperature is 600 ℃, and the calcining time is 4 hours.
In the present invention, Fe (NO) is used as a raw material3)3·9H2O、CH3COONa、NH4H2PO4Etc. providing an iron source, a sodium source and a phosphorus source for the material; the oxalic acid serving as the raw material is added in the synthesis process to be complexed with iron ions in an iron source, so that the phosphorus source, the iron source and the sodium source form a solution state, and the ionic state of the three elements is mixed. Forming a uniformly mixed precursor in the quick drying link of the spray drying technology, and performing subsequent dryingThe phosphorus source, the iron source and the sodium source can be quickly reacted and crystallized in the heat treatment crystallization link, so that the diffusion process in the crystallization process is shortened, and the crystallization efficiency is improved.
And adding a graphene dispersion liquid into the precursor synthesis solution, uniformly dispersing graphene in the solution through ultrasonic dispersion, and forming uniformly distributed precursors together with the phosphorus source, the iron source and the sodium source in a spray drying link. Meanwhile, in the drying process, the graphene exists in the spray droplets as a solid phase, a new phase carrier is provided for compounds in the droplets, the graphene is preferentially attached to the surface of the graphene, and uniformly compounded Na is formed in the subsequent heat treatment link3Fe2(PO4)(P2O7) @ Reduced graphene oxide composite.
Compared with the prior art, the invention has the advantages of rich raw material sources, low cost and simple preparation method. The prepared mixed polyanion material Na3Fe2(PO4)(P2O7) Because the electronic conductivity of the graphene oxide is not good, the research shows that in the structural framework of the polyanion compound, transition metal ions are often separated by polyanion groups which do not conduct electrons, and the electronic cloud of valence electrons of the transition metal ions is isolated to block the electronic exchange, so that the intrinsic electronic conductivity of the material is extremely low, and the practical application of the polyanion anode material is limited, therefore, the GO is modified by the GO, and during the calcining process, the GO is thermally Reduced into Reduced graphene oxide, so that the graphene layers which are mutually staggered can be loaded with Na in situ3Fe2(PO4)(P2O7) Particles, forming a conductive network, and finally obtaining Na with a three-dimensional micron spherical structure3Fe2(PO4)(P2O7) @ Reduced graphene composite. Na (Na)3Fe2(PO4)(P2O7) The @ Reduced graphene composite material can show excellent electrochemical performance as a positive electrode material of a sodium-ion battery.
Drawings
FIG. 1 shows Na of the present invention3Fe2(PO4)(P2O7) And Na3Fe2(PO4)(P2O7) The XRD pattern of @ rGO;
FIG. 2 shows Na of the present invention3Fe2(PO4)(P2O7) SEM picture of (1);
FIG. 3 shows Na of the present invention3Fe2(PO4)(P2O7) SEM picture of @ rGO;
FIG. 4 shows Na of the present invention3Fe2(PO4)(P2O7) And Na3Fe2(PO4)(P2O7) The @ rGO is used as a discharge specific capacity diagram of the positive electrode material of the sodium-ion battery under different multiplying powers;
FIG. 5 shows Na of the present invention3Fe2(PO4)(P2O7) @ rGO cycle performance plot at 20C rate.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
The following examples are specific for the treatment process:
1. therefore, the related medicines are all analytically pure;
2. the structure and the morphology of the material are characterized in that D8 ADVANCE (Brute, Germany) is adopted in X-ray diffraction, XRD analysis conditions are light Cu K α radiation, tube voltage is 40KV, scanning speed is 0.01 degree/s, scanning range is 8-70 degrees, and the models of scanning electron microscopes are JSM-7800F (Hitachi, Japan).
3. Assembling the battery: mixing an active substance material, carbon black and a binder polyvinylidene fluoride according to a mass ratio of 7: uniformly mixing the materials in a ratio of 2:1, wet-grinding the mixture for 2h at a rotating speed of 400rpm by using a planetary ball mill, taking out ball-milled beads, uniformly coating the ground materials on an aluminum foil sheet with a certain size, then placing the coated aluminum foil into an oven for further drying at a temperature of 120 ℃ for 8h, and finally cutting the dried aluminum foil sheet into straight pieces by using a cutting machineA circular pole piece with the diameter of 10 mm. The electrolyte is 1mol L-1NaClO4The volume ratio of the solvent is 1: 1 (EC) and diethyl carbonate (DEC). The metal sodium sheet is used as a counter electrode, the glass felt fiber is used as a battery diaphragm, and an R2016 type button battery is used for electrochemical test. The cell assembly was performed in a glove box filled with high purity argon.
4. The constant current charge and discharge test adopts a Wuhan blue battery test system CT 2001A. The charge-discharge voltage interval of the sodium ion battery is 1.5-3.5, and the charge-discharge current and the discharge specific capacity are calculated according to every 1mol of Na3Fe2(PO4)(P2O7) Two 2mol electron calculations (theoretical specific capacity of 119mAh g)-1). The cyclic voltammetry is tested by using Shanghai Chenghua CHI660C electrochemical workstation, and the voltage range is 1.5-3.5V (vs+). All electrochemical tests were performed at a constant temperature of 25 ℃.
The remainder, unless otherwise indicated, are all conventional commercial materials or conventional processing techniques in the art.
Example 1:
na synthesis by simple spray drying method3Fe2(PO4)(P2O7) A material. First, 8.08g of Fe (NO) was accurately weighed3)3·9H2Dissolving O in 400mL deionized water, adding 5g oxalic acid under magnetic stirring, and accurately weighing 2.46g CH after completely dissolving3COONa and 3.45g NH4H2PO4Separately added to the above solution (so that Fe is present3+、Na+And PO4 3+The molar ratio of the three ions is 2:3:3), and stirring is continued to obtain a clear solution. The clear solution was then passed through a spray dryer (220 ℃, 400r/min) to obtain a solid particulate precursor material. Finally, the obtained precursor material is put into a tube furnace, Ar-H2Atmosphere heat treatment (gas flow rate 20mL min)-1) Calcining at 600 ℃ for 4h to obtain Na3Fe2(PO4)(P2O7) A material.
Example 2:
na synthesis by simple spray drying method3Fe2(PO4)(P2O7) A @ reduced graphene oxide composite. First, 8.08g of Fe (NO) was accurately weighed3)3·9H2O (0.02mol) was dissolved in 400mL of deionized water, and 50mL of GO dispersion (5g/L) was added under magnetic stirring, followed by sonication in an ultrasonic instrument at a sonication frequency of 40000Hz for 1h so that GO was well dispersed in the solution. Then, 5g of oxalic acid was added to the above solution, and after completely dissolved, 2.46g of CH was accurately weighed out3COONa，3.45g NH4H2PO4Added separately to the above solution (to make Fe3+、Na+And PO4 3+The molar ratio of the three ions is 2:3:3), and after the three ions are completely dissolved, the precursor material in solid particle shape is obtained by a spray drier (220 ℃, 400 r/min). Finally, the obtained precursor material is put into a tube furnace, Ar-H2Atmosphere heat treatment (gas flow rate 20mL min)-1) Calcining at 600 ℃ for 4h to obtain the target product, namely Na3Fe2(PO4)(P2O7) @ reduced graphene oxide composite material (abbreviated as Na)3Fe2(PO4)(P2O7)@rGO)。
Na obtained in example 1 and example 23Fe2(PO4)(P2O7) And Na3Fe2(PO4)(P2O7) The XRD patterns of the @ rGO material are shown in figure 1, the diffraction peak shapes of the two materials are approximately same, and Na3Fe2(PO4)(P2O7) @ rGO material compared to Na3Fe2(PO4)(P2O7) The intensity of the diffraction peak is slightly stronger, which indicates that the crystallinity of the composite material is slightly better. In addition, we are right to Na3Fe2(PO4)(P2O7) The material was tested for ICP and the atomic ratio Na: Fe: P was 3.04:2: 2.95. SEM photographs of the two materials are shown in FIGS. 2 and 3, and in FIG. 2, Na is present3Fe2(PO4)(P2O7) The particles grow in an agglomerated manner and exhibit an irregular bulk structure, while in FIG. 3, Na3Fe2(PO4)(P2O7) The @ rGO material exhibits a regular three-dimensional microsphere structure. During the calcination process, GO can be reduced into rGO, active material particles can be dispersed and the growth of the active material particles can be limited, and an excellent conductive network can be formed to increase the electronic conductivity of the material. Na (Na)3Fe2(PO4)(P2O7) And Na3Fe2(PO4)(P2O7) The discharging specific capacity performance of the @ rGO serving as the positive electrode material of the sodium-ion battery under different multiplying rates is shown in figure 4. In FIG. 4, Na3Fe2(PO4)(P2O7) The specific discharge capacity of the material at 0.1C for the first time is 62.6mAh g-1Secondly, under the multiplying power of 0.2C, 0.5C, 1C, 5C, 10C and 20C, the specific discharge capacity is 57.1mAh g-1，51.8mAh g-1，45.8mAh g-1，40.4mAh g-1，27.1mAh g-1，18.2mAhg-1Modified Na as a comparison3Fe2(PO4)(P2O7) @ rGO material, under 0.1C, the first discharge specific capacity reaches 110.2mAh g-1And is 92.6% of the theoretical specific capacity. Then under the multiplying power of 0.2C, 0.5C, 1C, 5C, 10C and 20C, the specific discharge capacity is 105.6mAh g-1，99.7mAh g-1，93.4mAh g-1，83.8mAh g-1，73.9mAh g-1,59.7mAh g-1. In addition, in terms of cycle performance, as shown in FIG. 5, Na3Fe2(PO4)(P2O7) The retention rate of the discharging specific capacity of the @ rGO is still 89.68% after the @ rGO is circulated for 6400 times under the 20C discharging rate, and the coulomb efficiency is close to 100%.
Comparative example 1
The positive electrode material provided in this comparative example had Na as the main active ingredient4Fe3(PO4)2(P2O7) The preparation process is referred to the following documents: chen, W.Hua, J.Xiao, et al.NASICON-type air-table and all-climatecathode for sodium-ion batteries with low cost and high-power density[J].Nature Communications.2019,10:1480.
Also, it can be seen that the above-mentioned Na4Fe3(PO4)2(P2O7) The performance of the anode material is that the specific discharge capacity is 113.0mAh g under 0.05C multiplying power and 0.1C multiplying power respectively-1And 108.3mAh g-1In addition, under 20C multiplying power, 80.3mAh g still remains-1The specific discharge capacity of (2) was 69.1% after 4400 cycles.
Na in comparative example 1 above4Fe3(PO4)2(P2O7) Although the positive electrode material is under 0.05C multiplying power, the specific discharge capacity of the positive electrode material can reach 113mAh g-1However, at 20C rate, the retention rate of specific discharge capacity of the material after 4400 cycles is only 69.1%. By way of comparison, Na of the present application3Fe2(PO4)(P2O7) The retention rate of the specific discharge capacity of the cathode material is still 89.68% after the cathode material is cycled for 6400 times under the discharge rate of 20C. Therefore, at a larger discharge rate, Na of the present application3Fe2(PO4)(P2O7) The cathode material can show better electrochemical stability.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A mixed polyanion type positive electrode material of a sodium ion battery is characterized in that the positive electrode material is prepared by in-situ loading Na on a graphene layer3Fe2(PO4)(P2O7) And (4) particle composition.
2. The preparation method of the mixed polyanionic sodium-ion battery positive electrode material according to claim 1, which is characterized by comprising the following steps of:
(1) weighing Fe (NO)3)3·9H2Dissolving O solid in deionized water, adding oxalic acid, and adding CH3COONa and NH4H2PO4Stirring until the mixture is completely dissolved;
(2) drying the mixed solution obtained in the step (1) to obtain a precursor;
(3) placing the precursor obtained in the step (2) in Ar-H2Calcining under the atmosphere to obtain the target product.
3. The method for preparing the mixed polyanionic sodium-ion battery positive electrode material according to claim 2, wherein in the step (1), Fe (NO) is used3)3·9H2O、CH3COONa、NH4H2PO4The addition amount of (A) satisfies: fe3+、Na+And PO4 3+The molar ratio of the three ions was 2:3: 3.
4. The method for preparing the positive electrode material of the mixed polyanionic sodium-ion battery according to claim 2, wherein oxalic acid and Fe (NO) are used3)3·9H2The molar ratio of O is 2.5-3.5: 1.
5. the method for preparing the mixed polyanionic sodium-ion battery cathode material according to claim 2, wherein in the step (1), Fe (NO) is added before oxalic acid is added3)3·9H2And adding the graphene oxide dispersion liquid into the water solution of O.
6. The preparation method of the mixed polyanionic sodium-ion battery positive electrode material according to claim 5, wherein the concentration of the graphene oxide dispersion liquid is 5g/L, and the oxidized stone isGraphene dispersion with Fe (NO)3)3·9H2The addition ratio of O is 50mL-100 mL: 0.02 mol.
7. The preparation method of the mixed polyanionic sodium-ion battery cathode material according to claim 5, wherein the graphene oxide dispersion liquid is added, and then ultrasonic dispersion treatment is performed.
8. The method for preparing the mixed polyanionic sodium-ion battery cathode material according to claim 2, wherein in the step (2), the drying treatment process comprises the following steps: and (3) passing the mixed solution through a spray dryer, wherein the inlet temperature of the spray dryer is set to be 220 ℃, the outlet temperature of the spray dryer is set to be 80 ℃, and the rotating speed of the spray dryer is 400 r/min.
9. The method for preparing the mixed polyanionic sodium-ion battery positive electrode material according to claim 2, wherein in the step (3), Ar-H is adopted2In Ar and H2Is 95:5.
10. The method for preparing the mixed polyanionic sodium-ion battery cathode material according to claim 2, wherein in the step (3), the calcining temperature is 600 ℃ and the calcining time is 4 hours.
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