CN117790783B - Sodium ion battery positive electrode material and preparation method thereof - Google Patents
Sodium ion battery positive electrode material and preparation method thereof Download PDFInfo
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- CN117790783B CN117790783B CN202311822884.4A CN202311822884A CN117790783B CN 117790783 B CN117790783 B CN 117790783B CN 202311822884 A CN202311822884 A CN 202311822884A CN 117790783 B CN117790783 B CN 117790783B
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- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 29
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 51
- 239000007787 solid Substances 0.000 claims abstract description 33
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 21
- -1 transition metal salt Chemical class 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 15
- 239000011780 sodium chloride Substances 0.000 claims abstract description 13
- 239000008139 complexing agent Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 239000010405 anode material Substances 0.000 claims abstract description 9
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 8
- 230000032683 aging Effects 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims abstract description 7
- 239000010413 mother solution Substances 0.000 claims abstract description 6
- 238000001291 vacuum drying Methods 0.000 claims abstract description 6
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- 239000011734 sodium Substances 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 15
- 239000012452 mother liquor Substances 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 229910021389 graphene Inorganic materials 0.000 claims description 8
- 239000003273 ketjen black Substances 0.000 claims description 8
- 239000002041 carbon nanotube Substances 0.000 claims description 7
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- 238000010907 mechanical stirring Methods 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229920000388 Polyphosphate Polymers 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 239000001205 polyphosphate Substances 0.000 claims description 2
- 235000011176 polyphosphates Nutrition 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000000276 potassium ferrocyanide Substances 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- 239000000264 sodium ferrocyanide Substances 0.000 claims description 2
- GTSHREYGKSITGK-UHFFFAOYSA-N sodium ferrocyanide Chemical compound [Na+].[Na+].[Na+].[Na+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] GTSHREYGKSITGK-UHFFFAOYSA-N 0.000 claims description 2
- 235000012247 sodium ferrocyanide Nutrition 0.000 claims description 2
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 2
- 229940038773 trisodium citrate Drugs 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 21
- 238000000975 co-precipitation Methods 0.000 abstract description 12
- 239000007788 liquid Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000000376 reactant Substances 0.000 abstract description 6
- 238000001308 synthesis method Methods 0.000 abstract description 6
- 238000010899 nucleation Methods 0.000 abstract description 5
- 230000006911 nucleation Effects 0.000 abstract description 5
- 238000004090 dissolution Methods 0.000 abstract description 4
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 abstract description 3
- 229960003351 prussian blue Drugs 0.000 abstract description 3
- 239000013225 prussian blue Substances 0.000 abstract description 3
- 230000003993 interaction Effects 0.000 abstract description 2
- 229920001485 poly(butyl acrylate) polymer Polymers 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 230000007547 defect Effects 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000007791 liquid phase Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000004806 packaging method and process Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 206010042618 Surgical procedure repeated Diseases 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 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 1
- 241000080590 Niso Species 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000002572 peristaltic effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
-
- 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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- Battery Electrode And Active Subsutance (AREA)
Abstract
A positive electrode material of a sodium ion battery and a preparation method thereof belong to the technical field of Prussian blue preparation. The method comprises the following steps: uniformly mixing a carbon material with solid ferrocyanide and solid particles of transition metal salt according to a certain mass fraction, tabletting under a certain pressure, adding the mixture into mother solution (mixed solution of sodium chloride and complexing agent) at certain intervals and in a certain proportion, continuously introducing inert gas, continuously stirring, standing for a period of time after the mixture is completely added, collecting a sample, aging, centrifuging, and vacuum drying to obtain the sodium ion battery anode material. The solid-liquid coprecipitation method of the invention avoids the dissolution of reactants in water in an ionic form, effectively prevents the interaction of water and reactants, and only needs to dissolve NaCl and complexing agent in water, thereby reducing the use of water and effectively lowering the production cost. The present synthesis method gives the initial nucleation sites of PBAs by introducing carbon materials.
Description
Technical Field
The invention belongs to the technical field of Prussian blue preparation, and particularly relates to a sodium ion battery anode material and a preparation method thereof.
Background
The positive electrode material is an important component of the sodium ion battery, and Prussian blue materials (PBAs) have a plurality of advantages and become one of the positive electrode material selectable systems of the sodium ion battery with great application prospect. In the synthetic method, although the PBAs is a method with low cost, no pollution and high controllability, the method is difficult to synthesize in high concentration due to the limitation of the solubility of raw materials, and the problems of high sewage post-treatment cost, high equipment requirement and the like in the synthetic process of the method limit the application of the method in actual production. Meanwhile, although the solid phase method effectively avoids the use of water, the pure solid phase has the defects of insufficient reaction, easy impurity mixing and the like, so that high-quality crystals are difficult to synthesize, and the recycling performance is poor. In summary, the existing PBAs synthesis method generally results in higher material cost, poorer electrochemical performance and larger environmental hazard, and the invention is particularly proposed in view of the above.
Disclosure of Invention
The invention aims to solve the problems of high cost, poor electrochemical performance and the like of the existing PBAs synthesis method, and provides a sodium ion battery anode material and a preparation method thereof. The method is a brand-new coprecipitation method, improves the traditional liquid phase and solid phase coprecipitation, utilizes the solid-liquid reaction to prepare PBAs, and can improve the structural stability and electrochemical performance of the PBAs, thereby expanding the application of the PBAs as a positive electrode material of a sodium ion battery.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
A chemical formula of the positive electrode material of the sodium ion battery is A xB[Fe(CN)6]y·nH2 O, wherein A is Na and/or K, B is one or a combination of more than one of transition metals Sc, ti, V, cr, co, ni, cu, zn, ga, Y, zr, nb, mo, ru, rh, pd, ag, cd, in, sn, la, ce, pr, nd, sm, eu, gd, tb, dy, ho, er, tm and Yb, x is more than or equal to 1 and less than 2, y is more than or equal to 0 and less than or equal to 1, and n is more than or equal to 0 and less than or equal to 3.5.
The preparation method of the sodium ion battery anode material comprises the following steps: uniformly mixing a carbon material with solid ferrocyanide and solid particles of transition metal salt according to a certain mass fraction, tabletting under a certain pressure, adding the mixture into mother solution (mixed solution of sodium chloride and complexing agent) at certain intervals and in a certain proportion, continuously introducing inert gas, continuously stirring, standing for a period of time after the mixture is completely added, collecting a sample, aging, centrifuging, and vacuum drying to obtain the sodium ion battery anode material.
Further, the carbon material is one or a combination of more of graphene, graphite alkyne, carbon nanotube, porous carbon and ketjen black; the solid ferrocyanide salt is one or two of sodium ferrocyanide (Na 4[Fe(CN)6) and potassium ferrocyanide (K 4[Fe(CN)6), the transition metal salt is one or more of sulfate, hydrochloride or nitrate, and the mass ratio of the solid ferrocyanide salt to the transition metal salt is 1:1.
Further, the certain mass fraction is 0.01% -5.0%, more specifically, any value or range between any two values of 0.01%, 0.05%, 0.1%, 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, 4.5%, 5.0% may be selected.
Further, the method for uniformly mixing is one or a combination of a plurality of mechanical stirring method, air flow mixing method, swinging mixing method and vacuum mixing method.
Further, the certain pressure is 3 MPa-18 MPa, and more specifically can be selected from any value or range value between any two of 3MPa, 6MPa, 9MPa, 12MPa, 15MPa and 18 MPa; the certain time is 0.5 h-5 h, more specifically can be selected from any value or range value between any two of 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h and 5 h.
Further, the method is characterized in that the ferrocyanide salt and the transition metal salt are added into the mother liquor at the same time according to a certain proportion, and the amount of substances added each time is ensured to be the same, and the number of added tablets is 5: 25-1, further specifically selected to be any value or range between any two of 1:5, 1:4, 1:3, 1:2, 1:1, 2:1, 3:1, 4:1, 5:1.
Further, the complexing agent in the mother solution is one or a combination of several of trisodium citrate (C 6H5Na3O7), polyphosphate (Na 4P2O7) and ethylenediamine tetraacetic acid (EDTA); the mass ratio of the complexing agent in the mother solution to the substances of the transition metal salt is controlled between 1 and 6:1, further specifically may be selected to be any value or range between any two of 1:1, 2:1, 3:1, 4:1, 5:1, 6:1; the concentration of NaCl in the mother liquor is controlled to be 1-5 mol/L, more specifically, any value of 1mol/L, 2mol/L, 3mol/L, 4mol/L and 5mol/L or a range between any two of the values is selected.
Further, the stirring speed is 100-500 r/min, and more specifically can be selected from any value or a range between any two values of 100r/min, 150r/min, 200r/min, 250r/min, 300r/min, 350r/min, 400r/min, 450r/min and 500 r/min; the temperature of the vacuum drying is 100-200 ℃ and the time is 6-24 h. Specifically, the vacuum drying temperature may be selected from any value or range of values between any two of 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃; the drying time may be selected to be any value or range of values between any two of 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h.
Further, the reaction temperature for a period of time is 5-25 ℃, the aging temperature is 25-85 ℃, specifically, the reaction can be carried out at any value of 5 ℃,10 ℃, 15 ℃, 20 ℃ and 25 ℃ or a temperature range value between any two; the aging may be carried out at a temperature range of any one or both of 25 ℃,35 ℃, 45 ℃, 55 ℃,65 ℃, 75 ℃ and 85 ℃.
Compared with the prior art, the invention has the beneficial effects that:
(1) Compared with the traditional liquid phase reaction, the solid-liquid coprecipitation method avoids the dissolution of reactants in water in an ionic form, effectively prevents the interaction between water and the reactants, and only needs to dissolve NaCl and complexing agent in water, thereby reducing the use of water and effectively lowering the production cost.
(2) Compared with the traditional liquid phase reaction, the solid-liquid coprecipitation method has the advantages that the complexing agent is directly added into the base solution, so that the amount of the complexing agent is far greater than that of the transition metal salt, the amount of the complexing agent can be reduced, and the production cost is effectively reduced.
(3) Compared with the traditional liquid phase reaction, the solid-liquid coprecipitation method does not use peristaltic pumps, thereby reducing the cost of production equipment.
(4) The synthesis method uses environment-friendly materials, and produces less chemical sewage, so that the cost of sewage treatment is reduced, high-concentration synthesis can be realized, the synthesis space is reduced, and the synthesis efficiency is improved.
(5) The present synthesis method gives the initial nucleation sites of PBAs by introducing carbon materials. In addition, the hydrophobic nature of the carbon material may also create a localized "water-in-salt" reaction environment, reducing water ingress into the lattice.
(6) The synthesis method can effectively reduce the precipitation speed, so that the nucleation rate of the PBAs is slower, the PBAs is favorable for fully nucleation and growth of the PBAs, and the prepared PBAs particles have higher crystallinity, uniform size, regular morphology and lower defect and lattice water content, and are a sodium-rich positive electrode material, so that the PBAs have better stability and electrochemical performance.
Drawings
FIG. 1 is an XRD pattern of the PBAs material synthesized in example 1 of the present invention;
FIG. 2 is an SEM image of the synthesized PBAs material of example 1 of the present invention;
Fig. 3 is a graph showing the rate performance of PBAs materials synthesized in example 1 of the present invention in battery testing.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below in connection with the embodiments, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and all other embodiments obtained by persons skilled in the art without making creative efforts based on the embodiments in the present invention are within the protection scope of the present invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The technical problem to be solved by the invention is that the preparation method of PBAs for sodium ion batteries in the prior art has defects, such as too fast precipitation rate in the liquid phase coprecipitation process, so that the PBAs nucleate rate is too fast, and the prepared PBAs particles have the defects of low crystallinity, serious particle agglomeration, large amount of crystal lattice vacancies, water and the like, so that the performance of the anode material is affected. Aiming at the defects in the prior art, the invention aims to provide a brand-new coprecipitation method which can effectively reduce the precipitation rate, reduce the defects of PBAs and the crystallization water, improve the structural stability and the electrochemical performance to a certain extent and reduce the production cost.
In general, when a liquid phase coprecipitation method is adopted to prepare a sodium ion positive electrode material, the system has the defects of low crystallinity, serious particle agglomeration, large amount of crystal lattice vacancies, water and the like due to extremely high precipitation speed and over-high PBAs nucleation speed, so that the PBAs circulation stability is poor, the coulomb efficiency is low, the potential polarization is obvious and the like, and the application of the coprecipitation method in preparing the PBAs serving as the sodium ion battery positive electrode material is limited. In order to realize the reduction of the reaction rate in the coprecipitation process, the inventor provides a preparation method of PBAs serving as a positive electrode material of a sodium ion battery through long-term practice, namely a solid-liquid coprecipitation method. The main purpose is to reduce the precipitation rate, so that the crystal grains are fully grown, na + can fully enter the crystal lattice to replace the positions of vacancies and crystal water, thereby reducing the content of vacancy defects and crystal water and achieving the aim of increasing the chemical stability and electrochemical performance of PBAs.
Example 1
Step 1: 1mol of Na 4[Fe(CN)6 solid (about 303.910 g) is weighed, the weighed sample is processed into powder, then the sample is divided into 20 parts (0.05 mol per part and about 15.196 g), 20 parts of 0.1535g of graphene are weighed, the graphene is uniformly mixed by a mechanical stirring method, then the graphene is sequentially filled into a die (the mass fraction of the graphene in the mixture is 1%), the mixture is subjected to tabletting treatment by using 9MPa pressure, and the obtained 20 pieces of sample are put into a transparent packaging bag for use. Then 1mol of FeSO 4·7H2 O solid (about 278.01 g) was weighed out and the above procedure was repeated (mass per part of FeSO 4·7H2 O solid about 13.9005g, mass per part of graphene 0.1404g, mass fraction of graphene in the mixture 1%).
Step 2: 40mol of NaCl solid (about 2337.6 g) and 6mol of C 6H5Na3O7 solid (1764.6 g) were weighed and dissolved together in 20L of deionized water, and after complete dissolution, added to the reaction vessel, and stirred continuously at a stirring speed of 400 rpm. Then, an inert gas (nitrogen) was introduced, and the mixture was aerated for about 10 minutes.
Step 3: under the protection of nitrogen, adding Na 4[Fe(CN)6 pieces and FeSO 4·7H2 O pieces into the mother liquor at the same time, wherein the interval time is 2.5h. After the reactants are completely added, stirring is continued for 2 hours, and nitrogen is still required to be introduced into the reaction.
Step 4: after 2 hours, the resulting slurry was poured into a dish and aged at room temperature for 12 hours. The resulting slurry was centrifuged after the supernatant was removed, and the centrifuge was rotated at 10000 rpm for 3 minutes.
Step 5: and after complete centrifugation, placing the obtained material into an oven, and drying at 150 ℃ for 12 hours to obtain PBAs, namely the sodium ion battery anode material.
FIG. 1 shows an X-ray diffraction pattern of the PBAs material obtained in the present example, wherein the diffraction peak is identical to that of the standard card and has no impurity peak, which indicates that the synthesized material is pure phase PBAs, and the stronger diffraction peak indicates that the material has high crystallinity.
Fig. 2 is a scanning electron microscope image of the PBAs material synthesized in this example, and the morphology of the PBAs material is a regular cube with a size of about 0.5um, and the PBAs material is uniformly distributed.
Step 6: the preparation process of the positive electrode plate is adopted, and the positive electrode material is as follows: conductive carbon: mass ratio of PVDF binder = 7:2:1, a step of; the thickness of the positive pole piece is 130 mu m; the drying temperature is 150 ℃; the secondary drying time was 12h.
Fig. 3 shows the rate capability of the PBAs material synthesized in example 1 of the present application in a sodium ion battery, and it can be seen that the synthesized electrode has excellent rate capability, and the initial specific discharge capacity is up to 128.98mAh g -1 at a current density of 1C.
Example 2
Step 1: 2mol of K 4[Fe(CN)6 solid (about 736.68 g) is weighed, the weighed sample is processed into powder, then the sample is averagely divided into 40 parts (0.05 mol for each part and about 18.417 g), 40 parts of 0.5696g carbon nano tubes are weighed, uniformly mixed by an air flow mixing method, then the mixture is sequentially filled into a die, tabletting is carried out by using 18MPa pressure, and the obtained 40 samples are put into a transparent packaging bag for use. Then, 2mol of FeSO 4·7H2 O solid (about 556.02 g) was weighed, and the above operations were repeated (mass of FeSO 4·7H2 O solid was about 13.9005g per part, mass of carbon nanotubes was 0.4299g per part), and mass fractions of carbon nanotubes in the mixture were 3%.
Step 2: 80mol of NaCl solid (about 4675.2 g) and 10mol of C 6H5Na3O7 solid (about 2580.7 g) were weighed and dissolved together in 40L of deionized water, and stirred continuously at a stirring speed of 200 rpm.
Step 3: under the protection of nitrogen, adding Na 4[Fe(CN)6 pieces and FeSO 4·7H2 O pieces into the mother liquor at the same time, wherein each time, 2 pieces are added, and the interval time is 2 hours. After the reactants are completely added, stirring is continued for 2 hours, and nitrogen is still required to be introduced into the reaction.
The rest of the steps are the same as those of example 1
Example 3
Step 1: 2mol of Na 4[Fe(CN)6 solid (about 968.12 g) was weighed, the weighed sample was processed into powder, then the sample was divided equally into 40 parts (0.05 mol per part, about 24.203 g), then placed in a mold, subjected to tabletting treatment using 15MPa pressure, and the 40 obtained samples were put into a transparent packaging bag for use. Then 2mol of FeSO 4·7H2 O solid (about 556.02 g) was weighed, the above operation was repeated (mass of FeSO 4·7H2 O solid per part was about 13.9005 g), then 40 parts of carbon nanotubes were weighed, each part was 0.2112g, and after mixing uniformly, the mixture was put into a mold (mass fraction of carbon nanotubes in the mixture: 1.5%, and mold diameter: 5 cm).
Step 2: 80mol of NaCl solid (about 4675.2 g) and 12mol of C 6H5Na3O7 solid (about 3096.84 g) were weighed into 40L of deionized water and stirred continuously at a speed of 500 revolutions per minute, and Na 4[Fe(CN)6 and FeSO 4·7H2 O pieces were added simultaneously to the mother liquor, one at a time.
The rest of the steps are the same as those of example 1
Example 4
Step 1: 1mol of K 4[Fe(CN)6 (about 368.34 g) is weighed, the weighed sample is processed into powder, then the sample is divided into 50 parts (0.02 mol per part and about 7.3668 g) averagely, 50 parts (0.1534 g per part) of graphite alkyne are weighed, the mixture is uniformly mixed, the mixture is subjected to tabletting treatment by using 15MPa pressure, and the obtained sample is put into a transparent packaging bag for use. Then 1mol of MnSO 4·4H2 O (about 277.0 g) was weighed out, and the above operations were repeated (mass of 5.54g per part of MnSO 4·4H2 O and 0.1131g per part of graphite alkyne) and the mass fractions of graphite alkynes in the mixture were all 2%).
Step 2: 4mol of NaCl solid (about 233.76 g) and 6mol of C 6H5Na3O7 solid (about 1548.42 g) were weighed out and after complete reaction, aging was carried out at a temperature of 90 ℃.
The rest of the steps are the same as those of example 1
Example 5
Step 1: 1mol of Na 4[Fe(CN)6 (about 368.34 g) was weighed, the weighed sample was processed into powder, then the sample was equally divided into 40 parts (0.025 mol per part, about 9.2085 g), 40 parts (0.093 g per part by mass) of ketjen black was weighed, after being uniformly mixed, it was subjected to tabletting treatment using a pressure of 12MPa (mass fraction of ketjen black in the mixture: 1%), and the obtained sample was put into a transparent packaging bag for use. Then 1mol of FeSO 4·7H2 O (about 278.01 g) was weighed out, and the above operations were repeated (mass of FeSO 4·7H2 O per part was about 13.9005g, mass of Ketjen black per part was about 0.1404 g), and the mass fractions of Ketjen black in the mixture were 1%.
Step 2: under the protection of nitrogen, na 4[Fe(CN)6 pieces and FeSO 4·7H2 O pieces are added into the mother liquor simultaneously, and 2 pieces of Na 4[Fe(CN)6 and 1 piece of FeSO 4·7H2 O are added each time.
The rest of the steps are the same as those of example 1
Example 6
Step 1: 1.5mol of Na 4[Fe(CN)6 (about 552.51 g) was weighed, the weighed sample was processed into powder, then the sample was equally divided into 30 parts (0.05 mol per part, about 18.417 g), 30 parts (0.7674 g per part) of ketjen black were weighed, the mass fraction of ketjen black in the mixture was 4%, and after mixing uniformly, it was put into a mold, it was subjected to tabletting treatment using a pressure of 6MPa, and the obtained sample was put into a transparent package bag for use. Then 1.5mol of FeSO 4·7H2 O solid (about 417.015 g) was weighed out and the above procedure repeated (mass per part of FeSO 4·7H2 O solid about 13.9005 g).
Step 2: 60mol of NaCl solid (about 3506.4 g) and 10mol of C 6H5Na3O7 solid (about 2580.7 g) were weighed and dissolved together in 40L of deionized water, and after complete dissolution, added to the reaction vessel, and stirred continuously at a stirring speed of 500 rpm.
The rest of the steps are the same as those of example 1
Example 7
Step 1: 5mol of Na 4[Fe(CN)6 (about 1841.7 g) is weighed, the weighed sample is processed into powder, then the sample is divided into 50 parts (0.1 mol per part and about 36.834 g) averagely, 50 parts (1.9389 g per part) of porous carbon are weighed, the porous carbon is sequentially filled into a die after being uniformly mixed, tabletting is carried out on the porous carbon by using 18MPa pressure, and the obtained sample is put into a transparent packaging bag for use. Then 5mol of NiSO 4·7H2 O (about 2177.6 g) was weighed out and the above procedure repeated (43.552 g per FeSO 4·7H2 O mass and 2.292g per porous carbon mass); the mass fraction of porous carbon in the mixture was 5%.
Step 2: 200mol of NaCl solid (about 11688.0 g) and 30mol of C 6H5Na3O7 solid (about 4411.5 g) were weighed, dissolved in 100L of deionized water, and added at 5h intervals with stirring at 500 rpm, the remainder being the same as in example 1.
Step 3: the reaction temperature was set at 5 ℃.
The rest of the procedure is the same as in example 1.
TABLE 1
| Sample name | 1C Capacity (mAh/g) | Capacity retention after 400 cycles | First coulombic efficiency |
| Example 1 | 125 | 92％ | 99％ |
| Example 2 | 122 | 89％ | 98％ |
| Example 3 | 115 | 86％ | 98％ |
| Example 4 | 119 | 91％ | 97％ |
| Example 5 | 123 | 88％ | 99％ |
| Example 6 | 118 | 85％ | 99％ |
| Example 7 | 121 | 82％ | 98％ |
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (9)
1. A preparation method of a sodium ion battery anode material is characterized by comprising the following steps: the chemical formula of the positive electrode material of the sodium ion battery is A xB[Fe(CN)6]y·nH2 O, wherein A is Na and/or K, B is one or a combination of more than one of transition metal Sc, ti, V, cr, co, ni, cu, zn, ga, Y, zr, nb, mo, ru, rh, pd, ag, cd, in, sn, la, ce, pr, nd, sm, eu, gd, tb, dy, ho, er, tm and Yb, x is more than or equal to 1 and less than or equal to 2, y is more than or equal to 0 and less than or equal to 1, and n is more than or equal to 0 and less than or equal to 3.5;
The method comprises the following steps: uniformly mixing a carbon material with solid ferrocyanide and solid particles of transition metal salt according to a certain mass fraction, tabletting under a certain pressure, adding the mixture into mother liquor which is a mixed solution of sodium chloride and a complexing agent at certain intervals according to a certain proportion, continuously introducing inert gas, continuously stirring, standing for a period of time after the mixture is completely added, collecting a sample, aging, centrifuging, and vacuum-drying to obtain the sodium ion battery anode material; the above-mentioned method is characterized by that every time the ferrocyanide salt and transition metal salt are added into mother liquor at the same time, the quantity of every added material must be identical.
2. The method for preparing the positive electrode material of the sodium ion battery according to claim 1, wherein the method comprises the following steps: the carbon material is one or a combination of more of graphene, graphite alkyne, carbon nano tube, porous carbon and ketjen black; the solid ferrocyanide salt is one or two of sodium ferrocyanide and potassium ferrocyanide, the transition metal salt is one or more of sulfate, hydrochloride or nitrate, and the mass ratio of the solid ferrocyanide salt to the transition metal salt is 1:1.
3. The method for preparing the positive electrode material of the sodium ion battery according to claim 1, wherein the method comprises the following steps: the certain mass fraction is 0.01% -5.0%.
4. The method for preparing the positive electrode material of the sodium ion battery according to claim 1, wherein the method comprises the following steps: the method for uniformly mixing is one or a combination of a plurality of mechanical stirring method, air flow mixing method, swinging mixing method and vacuum mixing method.
5. The method for preparing the positive electrode material of the sodium ion battery according to claim 1, wherein the method comprises the following steps: the certain pressure is 3-18 MPa; the certain time is 0.5-5 h.
6. The method for preparing the positive electrode material of the sodium ion battery according to claim 1, wherein the method comprises the following steps: the number of sheets of each addition of the ferrocyanide salt and the transition metal salt was 5: 25-1.
7. The method for preparing the positive electrode material of the sodium ion battery according to claim 1, wherein the method comprises the following steps: the complexing agent in the mother solution is one or a combination of a plurality of trisodium citrate, polyphosphate and ethylenediamine tetraacetic acid; the mass ratio of the complexing agent in the mother solution to the substances of the transition metal salt is controlled to be 1-6: 1, the mass concentration of NaCl in the mother liquor is controlled to be 1-5 mol/L.
8. The method for preparing the positive electrode material of the sodium ion battery according to claim 1, wherein the method comprises the following steps: the stirring speed is 100-500 r/min; the temperature of the vacuum drying is 100-200 ℃ and the time is 6-24 hours.
9. The method for preparing the positive electrode material of the sodium ion battery according to claim 1, wherein the method comprises the following steps: the reaction temperature for a period of time is 5-25 ℃, and the aging temperature is 25-85 ℃.
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