CN115832289A - Flexible vanadium manganese sodium phosphate/carbon composite cathode material for sodium ion battery and preparation method thereof - Google Patents
Flexible vanadium manganese sodium phosphate/carbon composite cathode material for sodium ion battery and preparation method thereof Download PDFInfo
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 50
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- ZCZNSUUONOWGBP-UHFFFAOYSA-K P(=O)([O-])([O-])[O-].[Mn+2].[V+5].[Na+] Chemical compound P(=O)([O-])([O-])[O-].[Mn+2].[V+5].[Na+] ZCZNSUUONOWGBP-UHFFFAOYSA-K 0.000 title claims abstract description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 35
- 239000010406 cathode material Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000009987 spinning Methods 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011734 sodium Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 13
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 11
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 11
- 239000012528 membrane Substances 0.000 claims abstract description 11
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 9
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 9
- 229940091252 sodium supplement Drugs 0.000 claims abstract description 8
- 239000010405 anode material Substances 0.000 claims abstract description 7
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims abstract description 6
- 235000019837 monoammonium phosphate Nutrition 0.000 claims abstract description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- 239000011572 manganese Substances 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000003792 electrolyte Substances 0.000 claims description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 239000007774 positive electrode material Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000005245 sintering Methods 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical group O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 235000017281 sodium acetate Nutrition 0.000 claims description 5
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002228 NASICON Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- BDKLKNJTMLIAFE-UHFFFAOYSA-N 2-(3-fluorophenyl)-1,3-oxazole-4-carbaldehyde Chemical group FC1=CC=CC(C=2OC=C(C=O)N=2)=C1 BDKLKNJTMLIAFE-UHFFFAOYSA-N 0.000 claims description 2
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 claims description 2
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical group O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 2
- 229940087562 sodium acetate trihydrate Drugs 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 19
- 238000001354 calcination Methods 0.000 abstract description 4
- 230000005518 electrochemistry Effects 0.000 abstract description 3
- 238000005516 engineering process Methods 0.000 abstract description 2
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 abstract 1
- 229960002303 citric acid monohydrate Drugs 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 13
- 210000004027 cell Anatomy 0.000 description 12
- 239000004744 fabric Substances 0.000 description 9
- 238000004146 energy storage Methods 0.000 description 8
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 7
- 239000002134 carbon nanofiber Substances 0.000 description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 7
- 239000004698 Polyethylene Substances 0.000 description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 229920002239 polyacrylonitrile Polymers 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229940071125 manganese acetate Drugs 0.000 description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000004080 punching Methods 0.000 description 3
- 239000001632 sodium acetate Substances 0.000 description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
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- 238000007599 discharging Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
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- 150000002500 ions Chemical class 0.000 description 2
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- 239000007921 spray Substances 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
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- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
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- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000010416 ion conductor 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
- 238000004244 micellar electrokinetic capillary chromatography Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
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- 239000002985 plastic film Substances 0.000 description 1
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- 229920001155 polypropylene Polymers 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical group [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
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- 231100000419 toxicity Toxicity 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 239000012002 vanadium phosphate Substances 0.000 description 1
Images
Classifications
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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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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a flexible vanadium manganese sodium phosphate/carbon composite cathode material for a sodium ion battery and a preparation method thereof. Polyvinylpyrrolidone is dissolved in a proper amount of solvent under the condition of water bath or oil bath to obtain solution A; adding a vanadium source, a manganese source, a sodium source, ammonium dihydrogen phosphate and citric acid monohydrate into deionized water to form a solution B; slowly dripping the solution B into the solution A, and stirring to obtain a spinning solution; and (3) obtaining a flexible spinning membrane from the spinning solution through an electrostatic spinning technology, drying, and calcining to obtain the flexible self-supporting composite anode material. The self-supporting anode with mechanical flexibility and certain electrochemistry is prepared through electrostatic spinning, and meanwhile, the necessity of sodium supplement to the anode and the cathode in the practical application process of the sodium-ion battery is demonstrated by combining the cathode sodium supplement strategy, so that the potential wide application of the vanadium-based vanadium manganese phosphate sodium material in the field of the sodium-ion battery is effectively promoted.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a flexible vanadium manganese phosphate sodium/carbon composite cathode material for a sodium ion battery and a preparation method thereof.
Background
In order to reduce the pollution in the using process of the traditional fossil energy, the development of a novel chemical battery and a high-efficiency energy storage system has important significance. The sodium ion battery is considered to be the most possible to replace or supplement the lithium ion battery to become the next generation of novel energy storage battery due to the abundant sodium resource, low price and the similar working principle with the lithium ion battery. The electrochemistry and safety of energy storage cells depend primarily on both the electrode materials and the electrolyte used. The choice of electrode material, particularly the positive electrode material, largely determines the output voltage, the cycle performance, the safety and the battery cost (the positive electrode accounts for about 35-40% of the total battery cost). Currently, positive electrode materials of sodium ion batteries are mainly classified into the following four types: layered transition metal oxides, polyanionic compounds, organic compounds, and prussian blue analogs. The polyanion compound has the advantages of stable structure, small volume strain, fast ion diffusion and the like, and meets the actual requirements of the energy storage field. Sodium fast ion conductor (NASICON) type Na 3 V 2 (PO 4 ) 3 The lithium ion battery is considered to be a positive electrode material with great application potential due to the three-dimensional open structure, the rapid ion migration capability, the higher theoretical capacity and the proper working potential. However, the cost performance advantage of vanadium as an energy storage battery material is weakened due to the high cost and toxicity of vanadium. In order to further reduce the cost, a novel low-vanadium phosphate anode with long cycle stability and high energy density is developed, and the method has profound significance for large-scale energy storage application of the sodium-ion battery. Meanwhile, the development of flexible devices also puts new requirements on energy storage elements, and flexible sodium-ion batteries are still in the research and exploration stage at the present stage, so that the research on the synthetic method of the vanadium-based vanadium-manganese-sodium phosphate/carbon composite anode and the expansion of the application of the vanadium-based vanadium-manganese-sodium phosphate/carbon composite anode in the flexible energy storage devices are necessary.
Disclosure of Invention
The invention provides a preparation method of a flexible vanadium manganese sodium phosphate/carbon composite anode material for a sodium ion battery, which comprises the following steps:
(1) Adding a proper amount of polyvinylpyrrolidone into a certain amount of solvent to obtain a solution A;
(2) Weighing a vanadium source, a manganese source, a sodium source, ammonium dihydrogen phosphate and citric acid, adding deionized water, and stirring to obtain a solution B;
(3) Slowly dripping the solution B into the solution A, and stirring to obtain a spinning solution;
(4) Electrostatic spinning is carried out on the spinning solution to obtain a yellow-white flexible spinning film;
(5) And drying, pre-oxidizing and sintering the flexible spinning membrane at high temperature to obtain the black vanadium manganese sodium phosphate/carbon composite anode material.
Further, the solvent in the step (1) is at least one of deionized water or absolute ethyl alcohol.
Further, in the step (2), the vanadium source is vanadium pentoxide or ammonium metavanadate, the manganese source is manganese acetate tetrahydrate, and the sodium source is sodium acetate trihydrate.
Further, the operation of the step (4) is as follows: sucking 8mL of spinning solution, adjusting the voltage of an electrostatic spinning machine to be 25-28kV, the propelling flow rate to be 0.5-1mL/h, the collecting rotation speed to be 800rpm, the needle reciprocating distance to be 80-100mm, the needle outer diameter to be 0.4-1.0mm, and the distance between the needle and the collector to be 15cm.
Further, the flexible spinning membrane in the step (5) is pre-oxidized for 0.5 to 2 hours at the temperature of 250 to 300 ℃ in the air; the sintering temperature is 700-850 ℃, the sintering time is 6-12h, and the protective atmosphere is nitrogen or argon.
The invention provides a flexible vanadium manganese sodium phosphate/carbon composite cathode material for a sodium ion battery, which is prepared by the preparation method.
Further, the positive electrode material is in a NASICON type vanadium-based phosphate structure.
The invention provides a flexible sodium-ion battery which comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the positive electrode is made of the positive electrode material, and the positive electrode or the negative electrode of the battery is subjected to sodium supplement measures.
The invention has the beneficial effects that:
the self-supporting anode with electrochemistry and flexibility is constructed by combining the preparation technologies of electrostatic spinning and pre-oxidation, and the wide potential application of the vanadium-based vanadium-manganese-sodium phosphate material in the field of sodium ion batteries is promoted. And the necessity of sodium supplement to the positive electrode and the negative electrode in the practical application process of the sodium ion battery is explained by combining the positive electrode and negative electrode sodium supplement strategy.
The technical proposal of the invention provides a flexible self-supporting anode on one hand and provides the assembly application of the flexible sodium-ion battery on the other hand, and is expected to promote the practical process of the flexible sodium-ion battery.
Drawings
FIG. 1 is a photograph of a sample prepared in example 1;
FIG. 2 is a photograph of a sample prepared in example 2;
FIG. 3 is a circular pole piece cut from a sample prepared in example 1;
FIG. 4 is an XRD pattern of a sample prepared in example 1;
FIG. 5 is an SEM photograph of a sample prepared in example 1;
fig. 6 is a charge-discharge curve of the button sodium-ion half-cell composed of the composite positive electrode obtained in example 1 in example 5 at a rate of 0.2C;
FIG. 7 is the charge and discharge curve of the sodium ion full cell of the button of example 6 at 0.1C rate;
FIG. 8 is the charge-discharge curve at 0.1C rate for the coin-type sodium-ion full cell of example 7;
fig. 9 is the flexible soft package sodium-ion battery obtained in example 8;
fig. 10 is a charge and discharge curve of the flexible pouch battery obtained in example 8 at a rate of 0.2C.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention easier to understand, the present invention will be described in detail with reference to specific embodiments.
In the following examples, all reagents required are commercially available analytical grade. The electrospinning device used in the examples was a nano electrospinning machine NANON-01A produced by MECC, japan.
Example 1
The preparation method of the flexible vanadium manganese phosphate sodium/carbon composite cathode material for the sodium-ion battery comprises the following steps:
(1) Weighing 0.8g of polyvinylpyrrolidone (PVP) and 4mL of absolute ethyl alcohol, and magnetically stirring for 1h in an oil bath at 60 ℃ to obtain a solution A;
(2) 0.576g of citric acid was weighed and dissolved in 4mL of deionized water, 0.117g of ammonium metavanadate, 0.245g of manganese acetate, 0.345g of ammonium dihydrogen phosphate and 0.544g of sodium acetate were added in this order, and a solution B was obtained by magnetic stirring in an oil bath at 60 ℃. Slowly dripping the solution B into the solution A, and stirring at room temperature overnight to obtain a transparent spinning solution;
(3) The voltage of the electrostatic spinning machine is adjusted to be 28kV, the propelling flow rate is 0.5mL/h, the collecting rotating speed is 800rpm, the round-trip distance of the needle head is 80mm, the outer diameter of the needle head is 0.6mm, and the distance between the needle head and the tin foil collector is 15cm.
(4) Slowly stripping the spinning membrane from the tin foil paper, sequentially carrying out vacuum drying on the spinning membrane at 100 ℃, pre-oxidizing for 2h at 300 ℃ and calcining for 6h under the protection of nitrogen at 700 ℃ to obtain the vanadium manganese sodium phosphate/carbon composite cathode material (shown in figure 1).
Example 2
The preparation method of the flexible vanadium manganese phosphate sodium/carbon composite cathode material for the sodium-ion battery comprises the following steps:
this example is the same as example 1, except that the pre-oxidation process is omitted in step (4), and a vanadium manganese sodium phosphate/carbon composite positive electrode material (see fig. 2) is obtained.
Example 3
The preparation method of the flexible vanadium manganese phosphate sodium/carbon composite cathode material for the sodium-ion battery comprises the following steps:
(1) Weighing 3.0g of polyvinylpyrrolidone (PVP) and 15mL of deionized water, and magnetically stirring in a water bath at 80 ℃ for 2 hours to obtain a solution A;
(2) Weighing 2.306g of citric acid, dissolving into 8mL of deionized water, sequentially adding 0.468g of ammonium metavanadate, 0.980g of manganese acetate, 1.380g of ammonium dihydrogen phosphate and 2.177g of sodium acetate, and magnetically stirring to obtain a solution B. Slowly dripping the solution B into the solution A, and stirring overnight to obtain a transparent spinning solution;
(3) Two injectors are arranged on a spray head, 8mL of spinning solution is respectively absorbed, the voltage of an electrostatic spinning machine is adjusted to be 25kV, the propelling flow rate is 1.0mL/h, the collecting rotating speed is 800rpm, the reciprocating distance of a needle is 100mm, the outer diameter of the needle is 1.0mm, and the distance between the needle and a tin foil collector is 15cm.
(4) Slowly stripping the spinning film from the tin foil paper, sequentially performing vacuum drying on the spinning film at 100 ℃, pre-oxidizing at 280 ℃ for 1h, and calcining at 800 ℃ for 8h under the protection of argon gas to obtain the vanadium manganese sodium phosphate/carbon composite cathode material.
Example 4
The preparation method of the flexible vanadium manganese phosphate sodium/carbon composite cathode material for the sodium-ion battery comprises the following steps:
(1) Weighing 0.5g of polyvinylpyrrolidone (PVP) and 5mL of deionized water, and magnetically stirring in a water bath at 80 ℃ for 2 hours to obtain a solution A;
(2) 0.720g of citric acid is weighed and dissolved in 15mL of deionized water, 0.227g of vanadium pentoxide is added, water bath at 80 ℃ is carried out magnetic stirring, and the like to obtain a transparent solution, then the temperature is reduced to room temperature, and 0.613g of manganese acetate, 0.863g of ammonium dihydrogen phosphate and 0.820g of sodium acetate are sequentially added to obtain a solution B. Slowly dripping the solution B into the solution A, and stirring overnight to obtain a transparent spinning solution;
(3) Two injectors are arranged on a spray head, 8mL of spinning solution is respectively absorbed, the voltage of an electrostatic spinning machine is adjusted to be 25kV, the propelling flow rate is 0.8mL/h, the collecting rotating speed is 800rpm, the reciprocating distance of a needle is 100mm, the outer diameter of the needle is 0.8mm, and the distance between the needle and a tin foil collector is 15cm.
(4) Slowly stripping the spinning membrane from the tin foil paper, sequentially performing vacuum drying on the spinning membrane at 100 ℃, pre-oxidizing at 250 ℃ for 2h, and calcining at 750 ℃ for 12h under the protection of nitrogen to obtain the vanadium manganese sodium phosphate/carbon composite cathode material.
Example 5
The sodium ion battery of the embodiment comprises a positive electrode, a negative electrode, a diaphragm and electrolyte. The diaphragm is a glass cellulose membrane, and the electrolyte is 1M NaClO 4 Dissolving in ethylene carbonate/propylene carbonate (EC/PC, mass ratio 1Vinyl acetate (FEC) as an additive.
The preparation method of the sodium-ion battery comprises the following steps:
(1) The vanadium manganese phosphate sodium/carbon composite material obtained in example 1-4 was directly cut into an electrode having a diameter of 12mm by a punch to obtain a positive electrode sheet.
(2) And the counter electrode is a metal sodium sheet with the diameter of 14mm, and the button sodium-ion battery is assembled according to the assembly mode of the button battery in the prior art.
Example 6
The sodium ion battery of the embodiment comprises a positive electrode, a negative electrode, a diaphragm and electrolyte. The diaphragm is a polyethylene film (PE), and the electrolyte is 1M NaPF 6 Dissolved in ethylene carbonate/diethyl carbonate (EC/DEC, mass ratio 1), and 5% by mass of fluoroethylene carbonate (FEC) was added as an additive.
(1) The positive electrode is the vanadium manganese sodium phosphate/carbon composite material obtained in the example 1, and the composite material is cut into electrodes with the diameter of 12mm to obtain positive electrode sheets.
(2) And cutting the flexible carbon nanofiber cloth into electrodes with the diameter of 12mm to obtain the negative plate.
The flexible carbon nanofiber cloth is prepared by adopting a method comprising the following steps:
1.0g of Polyacrylonitrile (PAN) was dissolved in 10mL of N, N-Dimethylformamide (DMF), and 60 g of the solution was added o C stirring overnight to obtain a clear solution. The PAN electrospun fiber cloth is prepared in an electrostatic spinning mode, the working voltage is 18kV, and the product is received by tinfoil. And pre-oxidizing the collected PAN electrospun fiber cloth in air at 280 ℃ for 1h to obtain a stable structure, and then carbonizing in a tubular furnace under nitrogen to obtain the flexible carbon nanofiber cloth.
(3) The positive plate and the negative plate are respectively used as a positive electrode and a negative electrode, and 1M NaPF 6 The solution is used as electrolyte, PE is used as a diaphragm, and the button sodium ion full cell is assembled according to the assembly mode of the button cell in the prior art.
Example 7
The sodium ion battery of the embodiment comprises a positive electrode, a negative electrode, a diaphragm and electrolyte. The membrane is polyethyleneMembrane (PE) with 1M NaPF electrolyte 6 Dissolved in ethylene carbonate/diethyl carbonate (EC/DEC, mass ratio 1), and 5% by mass of fluoroethylene carbonate (FEC) was added as an additive.
(1) The anode is the vanadium manganese sodium phosphate/carbon composite material obtained in example 1, and Na with certain concentration is dripped on one surface of the material 2 C 2 O 4 And (3) drying the solution in vacuum, rolling, and finally punching the composite material into an electrode with the diameter of 12mm to obtain the positive plate.
(2) And punching the flexible carbon nanofiber cloth into an electrode with the diameter of 12mm to prepare the negative plate.
The above flexible carbon nanofiber cloth was obtained according to example 6.
(3) The positive plate and the negative plate are respectively used as a positive electrode and a negative electrode, and 1M NaPF 6 The solution is used as electrolyte, PE is used as a diaphragm, and the button sodium-ion battery is assembled according to the assembly mode of the button battery in the prior art.
Example 8
The sodium ion battery of the embodiment comprises a positive electrode, a negative electrode, a diaphragm and electrolyte. The diaphragm is a polypropylene film (PP), and the electrolyte is 1M NaClO 4 Dissolved in ethylene carbonate/diethyl carbonate (EC/DEC, mass ratio 1), and 2% by mass of fluoroethylene carbonate (FEC) was added as an additive.
(1) The anode was the sodium vanadium manganese phosphate/carbon composite obtained in example 1, and the composite was cut into 1X 2cm 2 And (5) preparing a positive plate by using a large and small rectangular plate.
(2) Cutting the flexible carbon nanofiber cloth into 1 × 2cm 2 And (3) dropping electrolyte on the rectangular sheet with the size, and directly short-circuiting the electrolyte with the metal sodium sheet to obtain the negative plate.
The above flexible carbon nanofiber cloth was obtained according to example 6.
(3) The positive plate and the negative plate are respectively used as a positive electrode and a negative electrode, a double-sided conductive copper foil tape is used as a positive electrode tab and a negative electrode tab, and 1M NaClO is used 4 The solution is used as electrolyte, PP is used as a diaphragm, and the flexible sodium ion battery is assembled according to the soft package assembly mode of the aluminum-plastic film in the prior art。
Test examples
(1) Physical Property test
1) Flexible detection
The flexibility of the vanadium manganese phosphate sodium/carbon composite cathode material prepared in the example 1 and 2 is compared, and as can be seen from the pictures, the flexibility of the sample obtained in the example 1 is better than that of the sample obtained in the example 2, the sample obtained in the example 1 can be punched into an electrode plate with the diameter of 12mm (see figure 3), and the edge of the sample obtained in the example 2 is easy to fall off in the punching process.
2) XRD test
XRD test is carried out on the vanadium manganese phosphate sodium/carbon composite positive electrode prepared in the example 1, and the result is shown in figure 4. As can be seen from figure 4, the product is mainly characterized by sodium vanadium manganese phosphate, with a peak value of 15-25 o The broad peak between the two is the characteristic peak of amorphous carbon, which indicates that the prepared material is vanadium manganese sodium phosphate/carbon composite material, and the carbon content is about 18% by thermogravimetric analysis.
3) SEM test
The sodium vanadium manganese phosphate/carbon composite positive electrode prepared in example 1 was subjected to SEM test, and the test results are shown in fig. 5. As can be seen from the figure, the composite anode material forms a porous network structure, one-dimensional structure of the composite anode material is convenient for electron transmission, the porous structure is favorable for sodium ions to be extracted and embedded, and the three-dimensional network structure enables the material to have certain flexibility.
(2) Electrochemical performance test
1) Half cell performance testing
Table 1 results of electrochemical performance tests of sodium ion half cells composed of the materials obtained in examples 1 to 4
| Specific discharge capacity (mAh/g) | First coulombic efficiency (%) | |
| Example 1 | 90 | 96.0 |
| Example 2 | 84 | 95.5 |
| Example 3 | 87 | 95.7 |
| Example 4 | 91 | 95.3 |
At room temperature, the button half-cell prepared in example 5 was subjected to a charge-discharge test at a charge-discharge current of 0.2C (22 mA/g), a charge cut-off voltage of 3.8V, and a discharge cut-off voltage of 2.5V, and the test results are shown in table 1. As can be seen from the table, the sodium ion half-cells obtained from the composite positive electrodes obtained in examples 1, 3 and 4 had a specific discharge capacity of substantially 90mAh/g, and the foregoing thermogravimetric analysis showed a carbon content of about 18%, which indicated that the capacity of the active material sodium vanadium manganese phosphate was about 110mAh/g, which was substantially close to its theoretical capacity of 111mAh/g. Meanwhile, the first charge-discharge coulombic efficiency of each material obtained in the embodiments 1-4 is higher, and is more than 95%, and the high coulombic efficiency is an important index of the material with practical application. In addition, the first three charge and discharge curves of the sodium ion battery made of the material obtained in example 1 are shown in fig. 6, and it can be seen from the graph that the first three charge curves of the battery almost coincide with each other, and the first three discharge curves also almost coincide with each other, which shows that the composite cathode material made of example 1 has good structural stability and flexibility. The material obtained in the embodiment 2 has low specific discharge capacity, and is a composite positive electrode material with poor flexibility due to omission of a pre-oxidation process, and the quality error caused by material falling easily at the edge of a pole piece in the battery manufacturing process. The higher specific discharge capacity of the composite cathode material obtained in example 4 is due to the higher crystallinity of the material caused by the higher sintering temperature and the longer sintering time. For battery materials, high crystallinity is beneficial to the capacity of the material, but too high a temperature and too long a heating time can lead to poor flexibility of the material.
2) Full battery performance test
The sodium ion full cell assembled in the button in example 6 was subjected to a charge and discharge test at a current density of 0.1C, and the charge and discharge cutoff voltage was 2.5 to 4.0V, and the obtained charge and discharge curve was as shown in fig. 7. It can be seen from the figure that the initial charging voltage of the full battery is low, the first reversible capacity is about 81mAh/g, the first charging and discharging coulombic efficiency is low, only 79%, which is mainly due to the problem of efficiency matching of the positive electrode and the negative electrode caused by the low first efficiency of the negative electrode material. The button full cell assembled in example 7 was also subjected to a charge and discharge test at a current density of 0.1C, and the first charge cut-off voltage was 4.3V, the discharge cut-off voltage was 2.5V, and thereafter the charge and discharge cut-off voltage was 2.5 to 4.0V, and the resulting charge and discharge curve was as shown in fig. 8. As can be seen from the figure, the first charge-discharge coulombic efficiency of the full cell is very low, mainly due to oxidative decomposition of sodium oxalate, which is a sodium supplement material, at higher voltages. In comparative example 6, the gram capacity of the material is slightly increased, and the first reversible capacity is about 85mAh/g, which shows that the addition of the sodium supplement material into the positive electrode material has a certain capacity increasing effect. The assembled flexible sodium ion full cell of example 8 (see fig. 9) was subjected to a charge and discharge test at a current density of 0.2C, and the charge and discharge cut-off voltage was 2.4 to 3.8V, and the resulting charge and discharge curve was shown in fig. 10. As can be seen from the figure, the first coulombic efficiency of the full cell is higher by about 92%, which is mainly due to the fact that the pre-sodium treatment is performed on the negative electrode, and therefore the first efficiency of the whole cell is improved. In addition, the first three-time charging and discharging curve of the flexible full battery is good in inosculation, and good cycling stability is indicated, so that a measure for supplementing sodium to a negative electrode or a positive electrode is taken into consideration in the practical application process of the sodium ion battery.
Claims (8)
1. A preparation method of a flexible vanadium manganese phosphate sodium/carbon composite positive electrode material for a sodium ion battery is characterized by comprising the following steps:
(1) Adding a proper amount of polyvinylpyrrolidone into a certain amount of solvent to obtain a solution A;
(2) Weighing a vanadium source, a manganese source, a sodium source, ammonium dihydrogen phosphate and citric acid, adding deionized water and stirring to obtain a solution B;
(3) Slowly dripping the solution B into the solution A, and stirring to obtain a spinning solution;
(4) Electrostatic spinning is carried out on the spinning solution to obtain a yellow-white flexible spinning film;
(5) And drying, pre-oxidizing and sintering the flexible spinning membrane at high temperature to obtain the black vanadium manganese sodium phosphate/carbon composite anode material.
2. The method for preparing the flexible vanadium manganese phosphate sodium/carbon composite cathode material for the sodium-ion battery according to claim 1, wherein the solvent in the step (1) is at least one of deionized water or absolute ethyl alcohol.
3. The method for preparing the flexible vanadium manganese phosphate sodium/carbon composite cathode material for the sodium-ion battery according to claim 1, wherein in the step (2), the vanadium source is vanadium pentoxide or ammonium metavanadate, the manganese source is manganese acetate tetrahydrate, and the sodium source is sodium acetate trihydrate.
4. The preparation method of the flexible vanadium manganese sodium phosphate/carbon composite cathode material for the sodium-ion battery, according to claim 1, is characterized in that the operation of the step (4) is as follows: sucking 8mL of spinning solution, adjusting the voltage of an electrostatic spinning machine to be 25-28kV, the propelling flow rate to be 0.5-1mL/h, the collecting rotation speed to be 800rpm, the needle reciprocating distance to be 80-100mm, the needle outer diameter to be 0.4-1.0mm, and the distance between the needle and the collector to be 15cm.
5. The preparation method of the flexible vanadium manganese sodium phosphate/carbon composite cathode material for the sodium-ion battery as claimed in claim 1, wherein in the step (5), the flexible spinning membrane is pre-oxidized in air at 250-300 ℃ for 0.5-2h; the sintering temperature is 700-850 ℃, the sintering time is 6-12h, and the atmosphere is nitrogen or argon.
6. A flexible vanadium manganese phosphate sodium/carbon composite anode material for a sodium ion battery is characterized in that: the positive electrode material is produced by the production method according to any one of claims 1 to 5.
7. The flexible vanadium manganese sodium phosphate/carbon composite positive electrode material for the sodium ion battery as claimed in claim 6, wherein the positive electrode material is of NASICON type vanadium-based phosphate structure.
8. A flexible sodium-ion battery, which comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, and is characterized in that the positive electrode of the battery is made of the positive electrode material of claim 7, and the positive electrode or the negative electrode of the battery is subjected to sodium supplement measures.
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| CN116826060A (en) * | 2023-08-29 | 2023-09-29 | 深圳海辰储能控制技术有限公司 | Composite sodium supplementing material, preparation method, positive pole piece, sodium battery and electric equipment |
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