CN111606314A - Preparation method of sodium vanadium sodium triphosphate as positive electrode material of sodium-ion battery - Google Patents
Preparation method of sodium vanadium sodium triphosphate as positive electrode material of sodium-ion battery Download PDFInfo
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 69
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 66
- -1 sodium vanadium sodium triphosphate Chemical compound 0.000 title claims abstract description 65
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 38
- 239000011734 sodium Substances 0.000 claims abstract description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 19
- 239000011737 fluorine Substances 0.000 claims abstract description 19
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 13
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 10
- 239000011574 phosphorus Substances 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 238000001291 vacuum drying Methods 0.000 claims abstract description 9
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 7
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 33
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 28
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 239000010406 cathode material Substances 0.000 claims description 16
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 16
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 238000005303 weighing Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 150000007524 organic acids Chemical group 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 239000011775 sodium fluoride Substances 0.000 claims description 8
- 235000013024 sodium fluoride Nutrition 0.000 claims description 8
- 238000005245 sintering Methods 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 claims description 6
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 6
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 229960002303 citric acid monohydrate Drugs 0.000 claims description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 6
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 6
- 150000003863 ammonium salts Chemical class 0.000 claims description 5
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical group S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 4
- JJEJDZONIFQNHG-UHFFFAOYSA-N [C+4].N Chemical compound [C+4].N JJEJDZONIFQNHG-UHFFFAOYSA-N 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 238000000498 ball milling Methods 0.000 claims description 4
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 4
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 3
- 239000001393 triammonium citrate Substances 0.000 claims description 3
- 235000011046 triammonium citrate Nutrition 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- BWKOZPVPARTQIV-UHFFFAOYSA-N azanium;hydron;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [NH4+].OC(=O)CC(O)(C(O)=O)CC([O-])=O BWKOZPVPARTQIV-UHFFFAOYSA-N 0.000 claims description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 2
- KLOIYEQEVSIOOO-UHFFFAOYSA-N carbocromen Chemical compound CC1=C(CCN(CC)CC)C(=O)OC2=CC(OCC(=O)OCC)=CC=C21 KLOIYEQEVSIOOO-UHFFFAOYSA-N 0.000 claims description 2
- OGUCKKLSDGRKSH-UHFFFAOYSA-N oxalic acid oxovanadium Chemical compound [V].[O].C(C(=O)O)(=O)O OGUCKKLSDGRKSH-UHFFFAOYSA-N 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 10
- 239000010405 anode material Substances 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000012535 impurity Substances 0.000 abstract description 4
- 208000028659 discharge Diseases 0.000 description 44
- 230000000052 comparative effect Effects 0.000 description 31
- 239000007788 liquid Substances 0.000 description 30
- 229960004106 citric acid Drugs 0.000 description 8
- 229910019142 PO4 Inorganic materials 0.000 description 7
- ZMVMBTZRIMAUPN-UHFFFAOYSA-H [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZMVMBTZRIMAUPN-UHFFFAOYSA-H 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- 229910001373 Na3V2(PO4)2F3 Inorganic materials 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000000725 suspension Substances 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- CFKDIWJRWVUNTF-UHFFFAOYSA-J [F-].[Na+].P(=O)([O-])([O-])[O-].[V+5] Chemical compound [F-].[Na+].P(=O)([O-])([O-])[O-].[V+5] CFKDIWJRWVUNTF-UHFFFAOYSA-J 0.000 description 3
- 230000003139 buffering effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229960004543 anhydrous citric acid Drugs 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000006179 pH buffering agent Substances 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/455—Phosphates containing halogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- 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
- H01M4/582—Halogenides
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Abstract
A preparation method of sodium vanadium phosphate trifluoride serving as a positive electrode material of a sodium-ion battery belongs to the technical field of battery material synthesis. The preparation method comprises the following steps: (1) dissolving raw materials such as a carbon source, a vanadium source, a phosphorus source, a fluorine source, a sodium source and the like; (2) removing free water under heating condition to obtain wet sol; (3) carrying out vacuum drying on the wet sol to obtain dry gel; (4) grinding the xerogel to obtain a powdery precursor; (5) and under the protection of flowing inert atmosphere, pre-burning and roasting the precursor, and cooling along with the furnace. The sodium vanadium sodium phosphate fluoride anode material of the sodium-ion battery prepared by the invention has high purity, and 3.3V (vs. Na) caused by impurity phases is eliminated+Na) and improves the work of the anode materialVoltage and energy density. The method has the advantages of simple operation and good reproducibility, and the prepared material has higher energy density and excellent multiplying power and cycle performance and can meet the requirements of practical application of the sodium-ion battery.
Description
Technical Field
The invention belongs to the technical field of battery material synthesis, and particularly relates to a preparation method of sodium vanadium phosphate trifluoride serving as a positive electrode material of a sodium-ion battery.
Background
Lithium ion batteries have become an ideal power source for portable electronic devices such as mobile phones, portable computers, and high-quality cameras because of their advantages such as high operating voltage, high energy density, and low environmental pollution. With the rise of the electric automobile industry, the demand of the lithium resources on which lithium ion batteries depend in the market is increased sharply, and the price of the lithium resources is rising continuously. The reserve of lithium is limited, and in the near future, problems of exhaustion of lithium resources and a rapid increase in price are bound to be encountered. Therefore, the development of high-efficiency energy storage materials and devices with abundant resources, low price, high safety and long service life is urgent.
In contrast, sodium element is low in price and abundant in reserves, and research, development and application of sodium ion batteries are beneficial to promoting development and innovation of large-scale energy storage technologies, so that the sodium ion batteries gradually become research hotspots in the field of energy storage. In terms of composition, the positive electrode material is a key part of the sodium ion battery, and largely determines the electrochemical properties such as capacity, working voltage, cycle life and the like of the whole battery system. In the existing research on positive electrode materials of sodium-ion batteries, polyanion type compound vanadium sodium trifluorophosphate (chemical formula is Na)3V2(PO4)2F3) The sodium ion battery anode material has more sodium storage vacancies and unobstructed sodium ion diffusion channels due to the open three-dimensional framework structure, so that the sodium ion battery anode material has higher specific capacity and better cycling stability. And, due to the introduction of fluorine element, the average working voltage of the sodium vanadium phosphate trifluoride is compared with that of sodium vanadium phosphate (chemical formula Na)3V2(PO4)3) An increase of about 300mV is obtained, which makes vanadium sodium trifluorophosphate available as a commercial sodium ionThe cell anode material has a wide application prospect, and therefore, the cell anode material also has wide attention.
Although the positive electrode material of the sodium-ion battery, namely the vanadium sodium triphosphate, has the advantages, most of research and reports at present contain impurities such as the vanadium sodium phosphate and other vanadium compounds in the prepared vanadium sodium triphosphate sample. The existence of these mixed phases will directly reduce the discharge capacity of the positive electrode material, and will also reduce the average working voltage that the positive electrode can exhibit to some extent, and thus reduce the energy density of the battery. Most of the literatures report that the prepared sodium vanadium triphosphate sample shows 3.6V (vs. Na) in a charge-discharge curve+Na) and 4.1V (vs. Na)+Na) of about 3.3V (vs. Na) can appear in addition to two discharge voltage platforms+Na), namely the embodiment of the hetero-phase sodium vanadium phosphate. In addition, although some documents prepare relatively pure sodium vanadium phosphate trifluoride samples, the low-voltage discharge plateau of about 3.3V in the charge-discharge curve cannot be completely eliminated, and the corresponding material synthesis method and the preparation process are often very complicated. Therefore, for the purpose of realizing higher energy density and better performance, a synthetic method with simple operation is needed to prepare the sodium vanadium sodium phosphate fluoride of the positive electrode material of the sodium-ion battery.
Disclosure of Invention
The invention provides a preparation method of sodium-ion battery cathode material vanadium sodium phosphate, aiming at solving the problems that the battery working voltage and energy density are reduced and the cycling stability is poor and the like caused by impure phase vanadium sodium phosphate generated by volatilization of fluorine element in the preparation process of the sodium-ion battery cathode material vanadium sodium phosphate+Na) and low working voltage platform.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of sodium vanadium phosphate trifluoride serving as a positive electrode material of a sodium-ion battery comprises the following steps:
the method comprises the following steps: dissolving carbon source in deionized water at room temperatureStirring and mixing uniformly to obtain a clear solution M1Regulating M1The pH of (A) is weakly acidic;
step two: weighing the carbon source in a molar ratio of 5: 2, adding it to solution M1In the method, stirring and heating are kept for 20-30 min to obtain a clear solution M2；
Step three: weighing a phosphorus source, a sodium source and a fluorine source, and adding the phosphorus source, the sodium source and the fluorine source into the solution M2Stirring and heating for 10-15 min to obtain clear solution M3；
Step four: keeping stirring and heating conditions unchanged to ensure that the solution M3The water in the solution is continuously evaporated, and the solution M is obtained after 8 to 12 hours3Gradually changing into black sol to finally form gel P1；
Step five: transferring the gel obtained in the fourth step into a vacuum drying oven for vacuumizing, heating and drying to obtain dry gel P2；
Step six: and D, taking out the dried gel obtained in the step V, grinding the dried gel by using a pestle or performing ball milling to obtain a powdery precursor, then putting the powdery precursor into a tube furnace, presintering the powdery precursor under the protection of flowing inert atmosphere to pyrolyze a carbon source, roasting the powdery precursor, and finally cooling the powdery precursor along with the furnace to obtain the sodium-ion battery cathode material, namely the sodium vanadium triphosphate.
Compared with the prior art, the invention has the beneficial effects that:
(1) the sodium ion battery anode material vanadium sodium trifluoride is prepared by a simple sol-gel method and a high-temperature solid phase sintering reaction, and 3.3V (vs. Na) caused by a vanadium sodium phosphate impurity phase is not reflected in a charge-discharge curve+Na) is adopted, and the average working voltage and energy density of the anode material are indirectly improved. Proved by facts, the specific energy of the first discharge of the positive electrode material of the sodium vanadium phosphate trifluoride ion battery prepared by the invention reaches 446.1mWh/g under the multiplying power of 1C, and the specific energy of the discharge can still reach 410.4mWh/g after 300 cycles of circulation. The specific energy of first discharge of the vanadium sodium phosphate fluoride prepared by the comparative example is 358.2mWh/g, and the specific energy of discharge after 300 cycles is only 289.5 mWh/g. In contrast, the energy density value of the sodium vanadium phosphate trifluoride prepared by the method is obviously improved。
(2) The preparation method has the advantages of easily available raw materials, simple operation, low cost and good reproducibility, and the prepared sodium ion battery cathode material vanadium sodium triphosphate has excellent multiplying power and cycle performance and can meet the requirements of practical application of the sodium ion battery. The fact proves that the initial discharge specific capacity of the positive electrode material of the sodium vanadium phosphate trifluoride ion battery under the multiplying power of 1C is 119.4mAh/g, and the value is close to the theoretical specific capacity (128.3 mAh/g). And after 300 cycles, the capacity retention rate reaches 92.4 percent, and the good cycle performance is shown. Meanwhile, under the high current density of 10C, the discharge specific capacity of the positive electrode material of the sodium vanadium phosphate trifluoride ion battery prepared by the invention can still reach 110.3mAh/g, and the excellent rate capability of the positive electrode material is shown.
(3) The invention optimizes the synthesis conditions and process parameters in the process of preparing the sodium vanadium phosphate trifluoride serving as the positive electrode material of the sodium-ion battery. Particularly, a strategy and an operation mode for adjusting the pH value of the precursor solution by adopting a carbon source with a pH buffering effect and changing the ratio of different types of carbon sources are provided, so that the operability of adjusting the pH value of the solution in a large amount of solution is improved.
Drawings
FIG. 1 is an X-ray diffraction pattern of the sodium vanadium phosphate trifluoride materials prepared in example 1 and comparative example 1;
FIG. 2 is a first charge-discharge cycle plot of the sodium vanadium phosphate trifluoride at a rate of 1C for the positive electrode material of the sodium-ion battery prepared in example 1;
FIG. 3 is a first charge-discharge cycle plot of sodium vanadium phosphate trifluoride at a 1C rate for the positive electrode material of the sodium-ion battery prepared in comparative example 1;
FIG. 4 is a first charge-discharge cycle plot of sodium vanadium phosphate trifluoride at a 1C rate for the positive electrode material of the sodium-ion battery prepared in comparative example 2;
FIG. 5 is a graph of differential capacity of the sodium vanadium sodium triphosphate of the positive electrode material of the sodium-ion battery prepared in example 1 in the first cycle at a magnification of 1C;
FIG. 6 is a graph of differential capacity of the sodium vanadium sodium fluorophosphate cathode material of the sodium-ion battery prepared in the comparative example 1 in the first cycle at a multiplying power of 1C;
FIG. 7 is a graph of differential capacity of the sodium vanadium sodium fluorophosphate cathode material of the sodium-ion battery prepared in the comparative example 2 in the first cycle at a magnification of 1C;
FIG. 8 is a graph of specific discharge capacity-cycle number performance at 1C rate for sodium vanadium phosphate trifluoride of the positive electrode materials of the sodium-ion batteries prepared in example 1, comparative example 1 and comparative example 2;
FIG. 9 is a graph of energy density-cycle number performance at 1C rate for sodium vanadium sodium phosphate fluoride of the positive electrode materials of the sodium-ion batteries prepared in example 1, comparative example 1 and comparative example 2;
fig. 10 is a graph of rate performance of sodium vanadium sodium trifluorophosphate as the positive electrode material for sodium-ion batteries prepared in example 1, comparative example 1 and comparative example 2.
Detailed Description
The technical solutions of the present invention are further described below with reference to the drawings and the embodiments, but the present invention is not limited thereto, and modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
The invention has the innovation points of controlling the roasting temperature of the material, adjusting the pH value of the precursor solution and reducing the volatilization of the fluorine element in the synthesis process. In the method, because the adjustment of the pH is often used in combination with a pH test paper or a pH meter, it is difficult to ensure that the pH of each part of the solution is consistent in practical operation. In this regard, the present invention proposes to adjust the pH of the precursor solution by dropping ammonia, and also proposes to directly add a carbon source having a pH buffering effect to adjust the pH. The added carbon source can be used as a coating material, a reducing agent and a chelating agent, and also can be used as a pH buffering agent, and the pH of the precursor solution can be regulated and controlled within a certain range by dripping ammonia water and changing the adding amount and proportion of different carbon sources.
The first embodiment is as follows: the present embodiment describes a method for producing sodium vanadium phosphate trifluoride as a positive electrode material for a sodium-ion battery, in which 3.3V (vs. na) due to impurity phases does not appear in a constant current charge-discharge curve of the obtained positive electrode material+/Na) Left and right discharge voltage plateaus, the method comprising the steps of:
the method comprises the following steps: dissolving a carbon source in deionized water at room temperature, and uniformly stirring and mixing to obtain a clear solution M1Regulating M1The pH of (A) is weakly acidic; in this step, the total molar amount of carbon source added is determined by the solution M1The limitation on the maximum dissolving amount of the raw materials is that the added carbon source and other raw materials (vanadium source, phosphorus source, sodium source and fluorine source) added later can be completely dissolved in the solution during the operation;
step two: weighing the carbon source in a molar ratio of 5: 2, adding it to solution M1In the method, stirring and heating are kept for 20-30 min to obtain a clear solution M2(ii) a The stirring and heating in the step are used for ensuring that the vanadium source can generate sufficient complex reaction with the added carbon source;
step three: weighing a phosphorus source, a sodium source and a fluorine source, and adding the phosphorus source, the sodium source and the fluorine source into the solution M2Stirring and heating for 10-15 min to obtain clear solution M3(ii) a The purpose of stirring and heating in this step is to enable the added raw materials to be sufficiently mixed and dissolved; the feeding sequence in the invention is related to the control of experimental conditions, the carbon source is dissolved first, so that the pH is adjusted later, and then the vanadium source is dissolved. After the vanadium source is dissolved, adding other raw materials at the back;
step four: keeping stirring and heating conditions unchanged to ensure that the solution M3The water in the solution is continuously evaporated, and the solution M is obtained after 8 to 12 hours3Gradually changing into black sol, and finally forming gel P containing small amount of water1；
Step five: transferring the gel obtained in the fourth step into a vacuum drying oven for vacuumizing, heating and drying to obtain dry gel P2；
Step six: taking out the xerogel in the fifth step, grinding the xerogel by a pestle or ball milling to obtain a powdery precursor, then putting the powdery precursor into a tube furnace, presintering the powdery precursor under the protection of flowing inert atmosphere to pyrolyze a carbon source, roasting the powdery precursor, and finally cooling the powdery precursor along with the furnace to obtain the positive electrode material of the sodium-ion batterySodium vanadium phosphate trifluoride. Has a chemical formula of Na3V2(PO4)2F3The mass percentage content is more than 95 percent.
The second embodiment is as follows: in the preparation method of sodium ion battery cathode material vanadium sodium phosphate trifluoride of the specific embodiment one, in the step one, the carbon source is organic acid and/or ammonium salt, and the organic acid is citric acid monohydrate and/or citric acid anhydrous; the ammonium salt is one or a mixture of more of ammonium dihydrogen citrate, diammonium hydrogen citrate and triammonium citrate. When the first and second carbon sources are added selectively, the acid and the acid ammonium salt can form a pH conjugated acid-base pair with a buffering effect in the solution.
The third concrete implementation mode: in the first step of the preparation method of sodium vanadium phosphate trifluoride as the positive electrode material of the sodium-ion battery, the weak acidity means that the pH is 3.0 to 5.0. The aim is to accelerate the complexation reaction in the second step, and inhibit the hydrolysis of fluorine and reduce the volatilization of fluorine.
The fourth concrete implementation mode: in a method for preparing sodium vanadium phosphate trifluoride as a positive electrode material of a sodium-ion battery, the adjustment of the solution to weak acidity includes two methods: firstly, ammonia water is directly dripped into the solution; and secondly, on the premise that the total amount of the carbon source to be added is selected in the step one, simultaneously selecting and adding an organic acid carbon source and an ammonium salt carbon source, and adjusting the proportion and the corresponding amount of the two carbon sources.
The fifth concrete implementation mode: in a method for preparing sodium vanadium phosphate trifluoride serving as a positive electrode material of a sodium-ion battery, a molar ratio of citrate in an organic acid carbon source to ammonium ions in an ammonium salt carbon source is 0.4 to 0.8.
The sixth specific implementation mode: in the second, third and fourth steps, in the process of removing a large amount of moisture in the precursor solution to obtain the sol, the heating condition is 45-75 ℃. The aim is to remove residual free water from the sol and at the same time reduce the volatilization of fluorine as much as possible.
The seventh embodiment: in a preparation method of sodium ion battery cathode material vanadium sodium triphosphate according to a specific embodiment, the vanadium source is one or a mixture of vanadium pentoxide, ammonium metavanadate and vanadyl oxalate; the phosphorus source is one or a mixture of more of ammonium dihydrogen phosphate, diammonium hydrogen phosphate and ammonium phosphate; the sodium source is one or a mixture of more of sodium fluoride, sodium acetate, sodium carbonate and sodium nitrate; the fluorine source is ammonium fluoride and/or sodium fluoride.
The specific implementation mode is eight: in a fifth step, the temperature of vacuum heating and drying is 60-80 ℃, the time is 6-12 hours, and the vacuum degree is 0.1MPa, so as to remove residual free water and reduce volatilization of fluorine elements in subsequent pre-sintering and roasting steps.
The specific implementation method nine: in the sixth step, the rotation speed of the ball mill is 200 to 300r/min, and the time is 10 to 15min, so as to grind the xerogel and reduce the volatilization of fluorine element.
The detailed implementation mode is ten: in the sixth step, the pre-sintering is carried out at the temperature of 250-350 ℃ for 4-8 hours, so as to fully pyrolyze the carbon source; the roasting temperature is 550-650 ℃, and the roasting time is 6-10 h, so that the carbothermic reduction reaction is fully performed, and the volatilization of fluorine elements is reduced; the temperature rise rate of the tubular furnace is set to be 5-10 ℃/min.
The concrete implementation mode eleven: in the sixth step of the preparation method of sodium vanadium phosphate trifluoride as the positive electrode material of the sodium-ion battery, the inert atmosphere is one of argon gas, nitrogen gas and hydrogen-argon mixed gas.
Example 1:
(1) according to the synthesis of 2mmol of the target product Na3V2(PO4)2F3Element group ofPreparing a sample according to the stoichiometric ratio. Firstly, 100mL of deionized water is measured, 0.6724g of citric acid monohydrate solid is added, and a clear citric acid solution is obtained after stirring and dissolving;
(2) adding ammonia water with the mass fraction of 20% into the citric acid solution dropwise under the monitoring of a pH meter until the pH of the solution is equal to 4.0;
(3) adding 0.364g of vanadium pentoxide into the solution after the pH is adjusted, keeping the temperature at 70 ℃, heating and stirring for 30 minutes, and sequentially changing yellow suspension into light yellow clarified liquid and light green clarified liquid;
(4) sequentially weighing 0.46g of ammonium dihydrogen phosphate and 0.252g of sodium fluoride, adding into the light green clarified liquid, and continuously heating and stirring at 70 ℃ for 15 minutes, wherein the light green clarified liquid is changed into a red brown clarified liquid;
(5) heating and stirring at 70 ℃, removing a large amount of water in the reddish brown clarified liquid, and obtaining viscous light green sol after about 8 hours;
(6) putting the light green sol into a vacuum drying oven, and drying for 6 hours at 70 ℃ in vacuum (0.1MPa) to obtain yellow green xerogel;
(7) after the xerogel is ground in a ball mill, it is transferred to a tube furnace. Under the protection of flowing high-purity argon, raising the temperature to 300 ℃ at the temperature raising rate of 5 ℃ per minute for pre-sintering for 4 hours, raising the temperature to 600 ℃ at the temperature raising rate of 5 ℃ per minute for roasting for 8 hours, and cooling along with the furnace to obtain the positive electrode material Na of the sodium-ion battery3V2(PO4)2F3。
The sodium ion battery anode material vanadium sodium triphosphate prepared in the embodiment is assembled to simulate a sodium ion battery, electrochemical performance test is carried out within a range of 2-4.3V, the first discharge specific capacity can reach 119.4mAh/g, the discharge specific capacity after 300 cycles can reach 110.4mAh/g, and the capacity retention rate is 92.4%. The specific capacities of the materials under 1C, 5C and 10C are 121.7 mAh/g, 118.3 mAh/g and 110.3mAh/g respectively.
Example 2:
(1) according to the synthesis of 4mmol of the target product Na3V2(PO4)2F3The elemental composition and the stoichiometric ratio of (a) were used to prepare samples. Firstly, measuring 30mL of deionized water, adding 0.336g of citric acid monohydrate solid and 1.1675g of triammonium citrate solid, and stirring for dissolving;
(2) adding 0.728g of vanadium pentoxide into the solution, keeping the temperature at 70 ℃, heating and stirring for 30 minutes, and sequentially changing yellow suspension into light yellow clarified liquid and light green clarified liquid;
(3) sequentially weighing 0.92g of ammonium dihydrogen phosphate and 0.454g of sodium fluoride, adding into the light green clarified liquid, continuously heating and stirring at 70 ℃ for 15 minutes, wherein the light green clarified liquid is changed into a red brown clarified liquid;
(4) heating and stirring at 70 ℃, removing a large amount of water in the reddish brown clarified liquid, and obtaining viscous light green sol after about 8 hours;
(5) putting the light green sol into a vacuum drying oven, and drying for 6 hours at 70 ℃ in vacuum (0.1MPa) to obtain yellow green xerogel;
(6) after the xerogel is ground in a ball mill, it is transferred to a tube furnace. Under the protection of flowing high-purity argon, raising the temperature to 350 ℃ at the temperature raising rate of 5 ℃ per minute for pre-sintering for 4 hours, raising the temperature to 600 ℃ at the temperature raising rate of 5 ℃ per minute for roasting for 10 hours, and cooling along with the furnace to obtain the positive electrode material Na of the sodium-ion battery3V2(PO4)2F3。
Example 3:
(1) according to the synthesis of 2mmol of the target product Na3V2(PO4)2F3The elemental composition and the stoichiometric ratio of (a) were used to prepare samples. Firstly, 100mL of deionized water is measured, 0.768g of anhydrous citric acid solid is added, and a clear citric acid solution is obtained after stirring and dissolving;
(2) adding ammonia water with the mass fraction of 20% into the citric acid solution dropwise under the monitoring of a pH meter until the pH of the solution is equal to or higher than 4.5;
(3) adding 0.364g of vanadium pentoxide into the solution after the pH is adjusted, keeping the temperature at 75 ℃, heating and stirring for 25 minutes, and sequentially changing yellow suspension into light yellow clarified liquid and light green clarified liquid;
(4) weighing 0.528g of diammonium hydrogen phosphate, 0.222g of ammonium fluoride and 0.318g of sodium carbonate in sequence, adding the diammonium hydrogen phosphate, the ammonium fluoride and the sodium carbonate into the light green clarified liquid, continuously keeping the temperature at 75 ℃, heating and stirring for 10 minutes, and observing that the light green clarified liquid is changed into a red brown clarified liquid;
(5) heating and stirring at 75 ℃ to remove a large amount of water in the reddish brown clarified liquid, and obtaining viscous light green sol after about 6 hours;
(6) putting the light green sol into a vacuum drying oven, and drying for 8 hours at 60 ℃ in vacuum (0.1MPa) to obtain yellow green xerogel;
(7) after the xerogel is ground in a ball mill, it is transferred to a tube furnace. Under the protection of flowing high-purity argon, heating to 350 ℃ at the heating rate of 8 ℃ per minute for pre-sintering for 4 hours, heating to 600 ℃ at the heating rate of 8 ℃ per minute for roasting for 9 hours, and cooling along with the furnace to obtain the Na-ion battery cathode material3V2(PO4)2F3。
Comparative example 1:
(1) according to the synthesis of 2mmol of the target product Na3V2(PO4)2F3The elemental composition and the stoichiometric ratio of (a) were used to prepare samples. Firstly, 100mL of deionized water is measured, 0.6724g of citric acid monohydrate solid is added, and a clear citric acid solution is obtained after stirring and dissolving;
(2) adding 0.364g of vanadium pentoxide into the citric acid solution, heating and stirring for 30 minutes at 70 ℃, and sequentially changing yellow suspension into light yellow clarified liquid and light green clarified liquid;
(3) sequentially weighing 0.46g of ammonium dihydrogen phosphate and 0.252g of sodium fluoride, adding into the light green clarified liquid, continuously heating and stirring at 75 ℃ for 10 minutes, wherein the light green clarified liquid is changed into a red brown clarified liquid;
(4) heating and stirring at 70 ℃, removing a large amount of water in the reddish brown clarified liquid, and obtaining viscous light green sol after about 8 hours;
(5) putting the light green sol into a vacuum drying oven, and drying for 6 hours at 70 ℃ in vacuum (0.1MPa) to obtain yellow green xerogel;
(6) after the xerogel is ground in a ball mill, it is transferred to a tube furnace. Under the protection of flowing high-purity argon, raising the temperature to 300 ℃ at the rate of 5 ℃ per minute for preburning for 3.5 hours, raising the temperature to 660 ℃ at the rate of 5 ℃ per minute for roasting for 8 hours, and cooling along with the furnace to obtain the Na-ion battery cathode material3V2(PO4)2F3。
The sodium ion battery anode material vanadium sodium phosphate fluoride prepared by the comparative example is assembled to simulate a sodium ion battery, electrochemical performance test is carried out within a range of 2-4.3V, the first discharge specific capacity can reach 102.4mAh/g, the discharge specific capacity after 300 cycles can reach 82.9mAh/g, and the capacity retention rate is 80.9%. The specific capacities of the materials are respectively 103.5 mAh/g, 63.2 mAh/g, 53.8mAh/g under 1C, 5C and 10C.
Comparative example 2:
(1) according to the synthesis of 2mmol of the target product Na3V2(PO4)2F3The elemental composition and the stoichiometric ratio of (a) were used to prepare samples. Firstly, 100mL of deionized water is measured, 0.6724g of citric acid monohydrate solid is added, and a clear citric acid solution is obtained after stirring and dissolving;
(2) adding ammonia water with the mass fraction of 20% into the citric acid solution dropwise under the monitoring of a pH meter until the pH of the solution is equal to or higher than 4.0;
(3) adding 0.364g of vanadium pentoxide into the solution after the pH is adjusted, keeping the temperature at 70 ℃, heating and stirring for 30 minutes, and sequentially changing yellow suspension into light yellow clarified liquid and light green clarified liquid;
(4) sequentially weighing 0.46g of ammonium dihydrogen phosphate and 0.252g of sodium fluoride, adding into the light green clarified liquid, continuously heating and stirring at 75 ℃ for 10 minutes, wherein the light green clarified liquid is changed into a red brown clarified liquid;
(5) heating and stirring at 70 ℃, removing a large amount of water in the reddish brown clarified liquid, and obtaining viscous light green sol after about 8 hours;
(6) putting the light green sol into a vacuum drying oven, and drying the light green sol in vacuum (0.1MPa) at 50 ℃ for 6 hours and then in vacuum at 70 ℃ for 6 hours to obtain yellow green xerogel;
(7) after the xerogel is ground in a ball mill, it is transferred to a tube furnace. Under the protection of flowing high-purity argon, raising the temperature to 300 ℃ at the rate of 5 ℃ per minute for preburning for 3.5 hours, raising the temperature to 660 ℃ at the rate of 5 ℃ per minute for roasting for 8 hours, and cooling along with the furnace to obtain the Na-ion battery cathode material3V2(PO4)2F3。
Comparative example 2 is different from example 1 in that the firing temperature after the calcination is 660 degrees celsius. The vanadium sodium phosphate trifluoride prepared by the comparative example is used as the positive electrode material of the sodium ion battery to assemble a simulated button sodium ion battery, electrochemical performance test is carried out within the range of 2-4.3V, the first specific discharge capacity can reach 119.0mAh/g, and the specific discharge capacity after 300 cycles is 99.0
mAh/g, the capacity retention ratio was 83.1%. The multiplying power performance test is carried out, and the discharging specific capacities under 1, 5 and 10C are respectively 118.0, 109.3 and 99.7 mAh/g.
FIG. 1 is an X-ray diffraction pattern of vanadium sodium triphosphate as a positive electrode material for sodium-ion batteries prepared in example 1 of the present invention and comparative example 1. As can be seen from FIG. 1, the product obtained in example 1 retains the structure of sodium vanadium triphosphate and has high purity and crystallinity. The X-ray diffraction spectrum of comparative example 1 showed some appearance of a few peaks and was relatively low in purity.
Fig. 2 is a first charge-discharge cycle curve of sodium vanadium phosphate trifluoride at a rate of 1C of the positive electrode material for the sodium-ion battery prepared in example 1 of the present invention. As shown in fig. 2, the primary discharge capacity of vanadium sodium phosphate fluoride as the positive electrode material of the sodium-ion battery obtained in example 1 was 119.4mAh/g when charge-discharge cycles were performed at 25 ℃ at a 1C rate in a voltage range of 2.0 to 4.3V. The first discharge capacity of comparative example 2 shown in FIG. 4 was 119.0 mAh/g. In contrast, comparative example 1 shown in FIG. 3 had a lower first discharge capacity of 102.4 mAh/g.
Fig. 5 is a differential capacity curve of the sodium vanadium sodium phosphate fluoride of the positive electrode material of the sodium-ion battery prepared in example 1 of the present invention, which is first cycled at a rate of 1C. From FIG. 5It is clear that 3.3V (vs. Na) is completely eliminated from the product obtained in example 1+Na) or so. While comparative example 1 shown in fig. 7 exhibited 3.3V (vs. na)+Na) and the phenomenon that the X-ray diffraction spectrum of the discharge platform shows a foreign peak. Comparative example 2 shown in fig. 7 also exhibited 3.3V (vs. na)+Na) or so. However, from the viewpoint of the discharge specific capacity corresponding to the plateau, 3.3V (vs. Na. of comparative example 2 shown in FIG. 4, compared to comparative example 1 shown in FIG. 3+Na) is small. These results indicate that in addition to the pH of the precursor solution, the firing temperature of the material, which affects 3.3V (vs. na), is one of the factors that affect the formation of the heterogeneous phase+Na) can be completely eliminated.
Fig. 8 is a specific capacity-cycle number performance curve of the sodium vanadium sodium phosphate fluoride battery cathode material prepared in example 1 of the present invention at a rate of 1C, wherein after 300 cycles, the discharge capacity is 110.4mAh/g, the capacity retention rate is 92.4%, and excellent cycle performance is shown. Compared with the comparative example 1, after the circulation is carried out for 300 circles, the discharge capacity is only 82.9mAh/g, the capacity retention rate is 80.9 percent, and the circulation performance is poor; the first discharge specific capacity of the comparative example 2 can reach 119.0mAh/g, the discharge specific capacity after 300 cycles is 99.0mAh/g, the capacity retention rate is 83.1%, and the cycle performance is relatively poor.
Fig. 9 is a discharge specific energy-cycle number performance curve of the sodium vanadium sodium phosphate fluoride battery cathode material prepared in example 1 of the present invention at a rate of 1C, wherein the first discharge specific energy is 446.1mWh/g, the discharge specific energy after 300 cycles is 410.4mWh/g, and the energy density is high. Comparative example 2 the specific energy of initial discharge was 443.0mWh/g, and the specific energy of discharge after 300 cycles was 359.6 mWh/g. While the specific energy of initial discharge of comparative example 1 was 358.2mWh/g, and the specific energy of discharge after 300 cycles was 289.5 mWh/g. In this view, the energy density of the sodium vanadium triphosphate obtained in example 1 was significantly improved compared to that obtained in comparative example 1.
Fig. 10 shows the capacity performance of the sodium vanadium phosphate trifluoride of the positive electrode material for the sodium-ion battery prepared in example 1 of the present invention at different multiplying factors. As shown in fig. 10, when the positive electrode material of the sodium-ion battery prepared in example 1 is charged and discharged at 1C, 5C and 10C rates, the specific discharge capacities of the vanadium sodium phosphate trifluoride are 121.7, 118.3 and 110.3mAh/g, respectively, and good rate capability is exhibited. In contrast, comparative example 1 has discharge specific capacities of 103.5, 63.2 and 53.8mAh/g at 1, 5 and 10C, respectively, and has relatively poor rate capability.
Claims (11)
1. A preparation method of sodium vanadium phosphate trifluoride serving as a positive electrode material of a sodium-ion battery is characterized by comprising the following steps of: the method comprises the following steps:
the method comprises the following steps: dissolving a carbon source in deionized water at room temperature, and uniformly stirring and mixing to obtain a clear solution M1Regulating M1The pH of (A) is weakly acidic;
step two: weighing the carbon source in a molar ratio of 5: 2, adding it to solution M1In the method, stirring and heating are kept for 20-30 min to obtain a clear solution M2；
Step three: weighing a phosphorus source, a sodium source and a fluorine source, and adding the phosphorus source, the sodium source and the fluorine source into the solution M2Stirring and heating for 10-15 min to obtain clear solution M3；
Step four: keeping stirring and heating conditions unchanged to ensure that the solution M3The water in the solution is continuously evaporated, and the solution M is obtained after 8 to 12 hours3Gradually changing into black sol to finally form gel P1；
Step five: transferring the gel obtained in the fourth step into a vacuum drying oven for vacuumizing, heating and drying to obtain dry gel P2；
Step six: and D, taking out the dried gel obtained in the step V, grinding the dried gel by using a pestle or performing ball milling to obtain a powdery precursor, then putting the powdery precursor into a tube furnace, presintering the powdery precursor under the protection of flowing inert atmosphere to pyrolyze a carbon source, roasting the powdery precursor, and finally cooling the powdery precursor along with the furnace to obtain the sodium-ion battery cathode material, namely the sodium vanadium triphosphate.
2. The method for preparing the sodium vanadium phosphate trifluoride of the positive electrode material of the sodium-ion battery according to claim 1, which is characterized in that: in the first step, the carbon source is organic acid and/or ammonium salt, and the organic acid is citric acid monohydrate and/or citric acid anhydrous; the ammonium salt is one or a mixture of more of ammonium dihydrogen citrate, diammonium hydrogen citrate and triammonium citrate.
3. The method for preparing the sodium vanadium phosphate trifluoride of the positive electrode material of the sodium-ion battery according to claim 1 or 2, characterized by comprising the following steps: in the first step, the weak acidity means that the pH is 3.0-5.0.
4. The preparation method of the sodium-ion battery cathode material vanadium sodium phosphate trifluoride according to claim 3, characterized by comprising the following steps: the means for adjusting the solution to a weakly acidic state include two: firstly, ammonia water is directly dripped into the solution; and secondly, on the premise that the total amount of the carbon source to be added is selected in the step one, the organic acid carbon source and the ammonium salt carbon source are simultaneously selected and added.
5. The preparation method of the sodium-ion battery cathode material vanadium sodium phosphate trifluoride according to claim 4, characterized by comprising the following steps: the molar ratio of citrate in the organic acid carbon source to ammonium ions in the ammonium salt carbon source is 0.4-0.8.
6. The method for preparing the sodium vanadium phosphate trifluoride of the positive electrode material of the sodium-ion battery according to claim 1, which is characterized in that: in the second, third and fourth steps, the heating condition is 45-75 ℃.
7. The method for preparing the sodium vanadium phosphate trifluoride of the positive electrode material of the sodium-ion battery according to claim 1, which is characterized in that: the vanadium source is one or a mixture of more of vanadium pentoxide, ammonium metavanadate and vanadyl oxalate; the phosphorus source is one or a mixture of more of ammonium dihydrogen phosphate, diammonium hydrogen phosphate and ammonium phosphate; the sodium source is one or a mixture of more of sodium fluoride, sodium acetate, sodium carbonate and sodium nitrate; the fluorine source is ammonium fluoride and/or sodium fluoride.
8. The method for preparing the sodium vanadium phosphate trifluoride of the positive electrode material of the sodium-ion battery according to claim 1, which is characterized in that: in the fifth step, the temperature of vacuum heating and drying is 60-80 ℃, the time is 6-12 hours, and the vacuum degree is 0.1 MPa.
9. The method for preparing the sodium vanadium phosphate trifluoride of the positive electrode material of the sodium-ion battery according to claim 1, which is characterized in that: in the sixth step, the rotation speed of the ball milling is 200-300 r/min, and the time is 10-15 min.
10. The method for preparing the sodium vanadium phosphate trifluoride of the positive electrode material of the sodium-ion battery according to claim 1, which is characterized in that: in the sixth step, the pre-sintering temperature is 250-350 ℃, and the time is 4-8 h; the roasting temperature is 550-650 ℃, and the roasting time is 6-10 h; the temperature rise rate of the tubular furnace is set to be 5-10 ℃/min.
11. The method for preparing the sodium vanadium phosphate trifluoride of the positive electrode material of the sodium-ion battery according to claim 1, which is characterized in that: in the sixth step, the inert atmosphere is one of argon, nitrogen and a hydrogen-argon mixed gas.
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|---|---|---|---|---|
| CN112186154A (en) * | 2020-09-23 | 2021-01-05 | 西安交通大学 | Sodium vanadium fluorophosphate @ CNTs composite material as well as preparation method and application thereof |
| CN114094066A (en) * | 2021-10-29 | 2022-02-25 | 江苏大学 | Sodium vanadium fluorophosphate/carbon cathode material, synthetic method thereof and sodium-ion battery |
| CN114824250A (en) * | 2022-01-17 | 2022-07-29 | 常州大学 | Multifunctional additive synchronously modified carbon-coated sodium vanadium fluorophosphate composite material, and preparation method and application thereof |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070160519A1 (en) * | 2005-03-28 | 2007-07-12 | Jeremy Barker | Method Of Making Active Materials For Use In Secondary Electrochemical Cells |
| CN103594716A (en) * | 2013-11-21 | 2014-02-19 | 天津工业大学 | Method for preparing cathode material of sodium-ion battery, namely sodium vanadium fluorophosphates |
| FR3042313A1 (en) * | 2015-10-13 | 2017-04-14 | Commissariat Energie Atomique | PROCESS FOR PREPARING AN NA3V2 (PO4) 2F3 PARTICULATE MATERIAL |
| WO2017124439A1 (en) * | 2016-01-18 | 2017-07-27 | 武汉理工大学 | Three-dimensional na3v2(po4)3 nanowire network electrode material, preparation method therefor and use thereof |
| CN107819115A (en) * | 2017-10-13 | 2018-03-20 | 北京科技大学 | A kind of fluorophosphoric acid vanadium sodium positive electrode of doping vario-property and preparation method thereof |
| CN107845796A (en) * | 2017-10-27 | 2018-03-27 | 东北大学秦皇岛分校 | A kind of carbon doping vanadium phosphate sodium positive electrode and its preparation method and application |
| CN108046231A (en) * | 2017-11-13 | 2018-05-18 | 中南大学 | A kind of sodium-ion battery positive material and preparation method thereof |
| CN109841802A (en) * | 2017-11-28 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of carbon coating Na3V2(PO4)2F3Compound and its preparation and application |
| WO2020030014A1 (en) * | 2018-08-07 | 2020-02-13 | 上海紫剑化工科技有限公司 | Vanadium sodium phosphate positive electrode material, sodium ion battery, preparation method therefor, and use thereof |
| CN111086978A (en) * | 2019-12-26 | 2020-05-01 | 中南大学 | Preparation method of sodium vanadium fluorophosphate cathode material |
| CN111162252A (en) * | 2019-12-23 | 2020-05-15 | 浙江大学 | Preparation method, product and application of RGO modified fluoro-substituted sodium vanadyl phosphate composite material |
-
2020
- 2020-06-04 CN CN202010501698.0A patent/CN111606314B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070160519A1 (en) * | 2005-03-28 | 2007-07-12 | Jeremy Barker | Method Of Making Active Materials For Use In Secondary Electrochemical Cells |
| CN103594716A (en) * | 2013-11-21 | 2014-02-19 | 天津工业大学 | Method for preparing cathode material of sodium-ion battery, namely sodium vanadium fluorophosphates |
| FR3042313A1 (en) * | 2015-10-13 | 2017-04-14 | Commissariat Energie Atomique | PROCESS FOR PREPARING AN NA3V2 (PO4) 2F3 PARTICULATE MATERIAL |
| WO2017124439A1 (en) * | 2016-01-18 | 2017-07-27 | 武汉理工大学 | Three-dimensional na3v2(po4)3 nanowire network electrode material, preparation method therefor and use thereof |
| CN107819115A (en) * | 2017-10-13 | 2018-03-20 | 北京科技大学 | A kind of fluorophosphoric acid vanadium sodium positive electrode of doping vario-property and preparation method thereof |
| CN107845796A (en) * | 2017-10-27 | 2018-03-27 | 东北大学秦皇岛分校 | A kind of carbon doping vanadium phosphate sodium positive electrode and its preparation method and application |
| CN108046231A (en) * | 2017-11-13 | 2018-05-18 | 中南大学 | A kind of sodium-ion battery positive material and preparation method thereof |
| CN109841802A (en) * | 2017-11-28 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of carbon coating Na3V2(PO4)2F3Compound and its preparation and application |
| WO2020030014A1 (en) * | 2018-08-07 | 2020-02-13 | 上海紫剑化工科技有限公司 | Vanadium sodium phosphate positive electrode material, sodium ion battery, preparation method therefor, and use thereof |
| CN111162252A (en) * | 2019-12-23 | 2020-05-15 | 浙江大学 | Preparation method, product and application of RGO modified fluoro-substituted sodium vanadyl phosphate composite material |
| CN111086978A (en) * | 2019-12-26 | 2020-05-01 | 中南大学 | Preparation method of sodium vanadium fluorophosphate cathode material |
Non-Patent Citations (3)
| Title |
|---|
| YING CHING等: ""Improved electrochemical performance of tin-sulfide anodes for sodium-ion batteries "", JOURNAL OF MATERIALS CHEMISTRY A * |
| 谷振一;郭晋芝;杨洋;吕红艳;赵欣欣;席晓彤;何晓燕;吴兴隆;: "钠离子电池正极材料Na_3V_2(PO_4)_2O_2F的控制合成与电化学性能优化", 无机化学学报 * |
| 阙兰芳等: "具有可控形貌和晶格结构的自支撑钛酸纳米阵列钠电负极", 第18届全国固态离子学学术会议暨国际电化学储能技术论坛论文集 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112186154A (en) * | 2020-09-23 | 2021-01-05 | 西安交通大学 | Sodium vanadium fluorophosphate @ CNTs composite material as well as preparation method and application thereof |
| CN114094066A (en) * | 2021-10-29 | 2022-02-25 | 江苏大学 | Sodium vanadium fluorophosphate/carbon cathode material, synthetic method thereof and sodium-ion battery |
| CN114824250A (en) * | 2022-01-17 | 2022-07-29 | 常州大学 | Multifunctional additive synchronously modified carbon-coated sodium vanadium fluorophosphate composite material, and preparation method and application thereof |
| CN114824250B (en) * | 2022-01-17 | 2024-05-03 | 常州大学 | Multifunctional additive synchronous modified carbon-coated vanadium sodium fluorophosphate composite material, preparation method and application thereof |
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