CN115744866A - Vanadium sodium fluorophosphate material synthesized by instantaneous Joule heat sintering and preparation method and application thereof - Google Patents
Vanadium sodium fluorophosphate material synthesized by instantaneous Joule heat sintering and preparation method and application thereof Download PDFInfo
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- CN115744866A CN115744866A CN202211085538.8A CN202211085538A CN115744866A CN 115744866 A CN115744866 A CN 115744866A CN 202211085538 A CN202211085538 A CN 202211085538A CN 115744866 A CN115744866 A CN 115744866A
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- 239000000463 material Substances 0.000 title claims abstract description 49
- CHQMXRZLCYKOFO-UHFFFAOYSA-H P(=O)([O-])([O-])F.[V+5].[Na+].P(=O)([O-])([O-])F.P(=O)([O-])([O-])F Chemical compound P(=O)([O-])([O-])F.[V+5].[Na+].P(=O)([O-])([O-])F.P(=O)([O-])([O-])F CHQMXRZLCYKOFO-UHFFFAOYSA-H 0.000 title claims abstract description 32
- 238000005245 sintering Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000000843 powder Substances 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000011734 sodium Substances 0.000 claims abstract description 19
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 14
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 14
- 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
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 13
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 13
- 238000000713 high-energy ball milling Methods 0.000 claims abstract description 13
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 13
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011737 fluorine Substances 0.000 claims abstract description 12
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 12
- 239000011574 phosphorus Substances 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 12
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 12
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 12
- -1 vanadium sodium fluorophosphate compound Chemical class 0.000 claims abstract description 11
- 239000007774 positive electrode material Substances 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 239000012002 vanadium phosphate Substances 0.000 claims description 13
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000010406 cathode material Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 8
- 230000008859 change Effects 0.000 claims description 8
- 239000004744 fabric Substances 0.000 claims description 8
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- GLMOMDXKLRBTDY-UHFFFAOYSA-A [V+5].[V+5].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [V+5].[V+5].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GLMOMDXKLRBTDY-UHFFFAOYSA-A 0.000 claims description 7
- 239000000853 adhesive Substances 0.000 claims description 7
- 230000001070 adhesive effect Effects 0.000 claims description 7
- 239000010452 phosphate Substances 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 238000009529 body temperature measurement Methods 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- 235000013024 sodium fluoride Nutrition 0.000 claims description 4
- 239000011775 sodium fluoride Substances 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- 239000011164 primary particle Substances 0.000 claims description 3
- 239000011163 secondary particle Substances 0.000 claims description 3
- 238000003746 solid phase reaction Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-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
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 2
- 229940039790 sodium oxalate Drugs 0.000 claims description 2
- 238000001931 thermography Methods 0.000 claims description 2
- 238000005485 electric heating Methods 0.000 claims 3
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000000498 ball milling Methods 0.000 description 13
- 238000001816 cooling Methods 0.000 description 7
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 239000010959 steel Substances 0.000 description 6
- 239000010405 anode material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 238000000840 electrochemical analysis Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 229920000447 polyanionic polymer Polymers 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
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- 238000004729 solvothermal method Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
Images
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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
Abstract
The invention provides a vanadium sodium fluorophosphate material synthesized by instantaneous joule heating sintering and a preparation method and application thereof, wherein a vanadium source, a phosphorus source, a fluorine source and a sodium source are respectively placed at room temperature of 15-35 ℃ for high-energy ball milling and then mixed, or the vanadium source, the phosphorus source, the fluorine source and the sodium source are mixed and then placed at room temperature of 15-35 ℃ for high-energy ball milling, and a ball-milled mixture is obtained; transferring the mixture to an electrothermal conversion medium in a reactor under inert atmosphere, operating a function program of current and voltage changing along with time by using a joule heat sintering synthesis device, and collecting product powder from the reactor after the synthesis process is finished; and washing, filtering and drying the product powder to obtain the sodium vanadium fluorophosphate material. The vanadium sodium fluorophosphate compound prepared by the method is used as a positive electrode material to show higher specific capacity, excellent cycle stability and rate capability in a sodium ion battery, and realizes the ultra-fast and low-energy-consumption synthesis of the high-performance sodium ion battery positive electrode material.
Description
Technical Field
The invention relates to the field of high-performance positive electrode materials of sodium-ion batteries, in particular to a vanadium sodium fluorophosphate material synthesized by instantaneous joule heating sintering and a preparation method and application thereof.
Background
Sodium ion batteries have received great attention due to the widespread distribution of sodium and the similar energy storage mechanisms of lithium ion batteries. However, their commercial use is often hampered by the relatively high production costs and poor performance of compound cathode materials. Due to the induction effect of the polyanion group, the polyanion compound cathode material has higher oxidation-reduction potential, and the stable three-dimensional framework of the polyanion compound cathode material also obviously reduces the structural change of sodium ion deintercalation. In addition, the existence of strong covalent bond can effectively inhibit the oxygen extraction. These advantages lead to excellent cycling stability and high safety of the polyanionic materials.
Vanadium sodium fluorophosphate is recognized as a promising positive electrode material of a sodium-ion battery due to high working potential and high energy density. The F-V bond has strong ionic property, so that the material has high output voltage, and in a typical charge-discharge curve, 3.7V and 4.2V voltage platforms exist, which respectively correspond to the extraction or the insertion of sodium ions at different sites, and the theoretical energy density higher than 500Wh/kg is realized.
At present, the preparation method of the sodium vanadium fluorophosphate electrode material mainly comprises a solid phase method, a water/solvothermal method, a coprecipitation method, a sol-gel method and the like, although the target material with higher purity can be successfully prepared, the energy consumption and the cost are greatly increased in large-scale preparation due to longer heat preservation time in the high-temperature calcination process, and the water/solvothermal method can reduce the reaction temperature but cannot realize batch production due to lower yield and high equipment requirement. Therefore, it is particularly important for practical production to explore a fast synthesis method with high heating rate and low time scale, which is easy to realize and has economic benefits.
Disclosure of Invention
The invention overcomes the defects in the prior art, and provides a vanadium sodium fluorophosphate material synthesized by instantaneous joule heating sintering, a preparation method and application thereof.
The purpose of the invention is realized by the following technical scheme.
An instantaneous Joule heat sintering synthesis method of a sodium vanadium fluorophosphate material, wherein the chemical formula of a sodium vanadium fluorophosphate compound in the sodium vanadium fluorophosphate material is Na 3 (VO 1-x PO 4 ) 2 F 1+2x (x is more than or equal to 0 and less than or equal to 1), the material has the shape characteristic of lamellar, the average grain diameter of primary particles in the material is 500nm, the average grain diameter of secondary particles in the material is 1 mu m, and the 0.1C specific discharge capacity of the material is 135mAhg -1 The 1C specific discharge capacity of the material is 122mAhg -1 And 94.1% of theoretical specific capacity can be achieved.
A preparation method for synthesizing a sodium vanadium fluorophosphate material by instantaneous Joule thermal sintering comprises the following steps:
step 1, respectively placing a vanadium source, a phosphorus source, a fluorine source and a sodium source at room temperature of 15-35 ℃ for high-energy ball milling and then mixing, or mixing the vanadium source, the phosphorus source, the fluorine source and the sodium source and then placing at room temperature of 15-35 ℃ for high-energy ball milling to obtain a ball-milled mixture, wherein the stoichiometric ratio of the vanadium source to the phosphorus source to the fluorine source to the sodium source is 2, (0-3) to 3, excluding 0;
and 3, washing, filtering and drying the product powder prepared in the step 2 to obtain the sodium vanadium fluorophosphate material.
In the step 1, one or more of vanadium pentoxide, ammonium metavanadate, vanadyl phosphate and vanadium phosphate is adopted as a vanadium source, one or more of diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphate, vanadyl phosphate and vanadium phosphate is adopted as a phosphorus source, one or more of sodium fluoride, sodium carbonate, sodium bicarbonate, sodium acetate and sodium oxalate is adopted as a sodium source, one or two of ammonium fluoride and sodium fluoride is adopted as a fluorine source, and the stoichiometric ratio of the vanadium source to the phosphorus source to the fluorine source to the sodium source is 2 (1-3): 3.
In the step 1, the high-energy ball milling time is 12-24h, and the room temperature is 25 ℃.
In the step 2, the inert atmosphere is one or more of argon, nitrogen and helium, preferably argon.
In step 2, the joule heating sintering synthesizer comprises a power supply module, a reactor module and a temperature measuring module,
the power supply module is a direct-current programmable power supply, and regulates and controls the energy and temperature change of a load on an electrothermal conversion medium by programming a function program of current and voltage changing along with time, wherein the function program comprises one or more of sine waves, rectangular waves, sawtooth waves, triangular waves and step waves;
the reactor module comprises a conductive connecting piece and an electrothermal conversion medium, wherein the conductive connecting piece is used for fixing the electrothermal conversion medium and comprises one or more of conductive copper adhesive and conductive silver adhesive, the electrothermal conversion medium is used for realizing high-efficiency and limited-range conversion of electric energy and heat energy and providing energy required by solid-phase reaction for precursor powder and comprises one or more of carbon cloth, carbon felt, nickel foil, cobalt foil and iron foil;
the temperature measuring module is used for recording the temperature change along with time in the reaction process, and adopts a non-contact temperature measuring device which comprises one or more of an infrared temperature measuring device, a laser temperature measuring device and a thermal imaging temperature measuring device;
the electric heat conversion medium is arranged on two sides of the electric heat conversion medium and is connected with the power supply module through a lead, and the temperature measurement module is arranged above the electric heat conversion medium.
In the step 2, during the Joule thermal sintering synthesis reaction, the power supply open circuit voltage is 20-40V, the current is 10-50A, the reaction time is 2-60s, the electrothermal conversion medium adopts cobalt foil, nickel foil or electrochemical carbon cloth, and the electrothermal conversion medium adopts a rectangular structure with the thickness of 0.01-0.5mm and the thickness of (5-6) × (2-2.5) cm.
In the step 3, the stirring speed in the water washing process is 500-1000r/min, and the stirring time is 1-12h.
In step 3, the drying temperature is 40-100 ℃, preferably 60 ℃ and the drying time is 6-12h, preferably 12h.
The invention provides a positive electrode material of a sodium-ion battery, which is prepared from a sodium vanadium fluorophosphate material.
The invention provides a battery anode which is prepared from a sodium-ion battery anode material serving as a raw material.
The invention provides a battery, which comprises a battery anode prepared from a sodium-ion battery anode material.
After loading the precursor sample on an electrothermal conversion medium in a reactor module, operating a function program of current and voltage changing along with time, starting an instantaneous joule heating sintering process, and collecting a product from the reactor after the synthesis process is finished, thereby obtaining the target sample material.
The invention has the beneficial effects that: the vanadium sodium fluorophosphate compound prepared by the method is used as a positive electrode material to show higher specific capacity, excellent cycling stability and rate capability in a sodium ion battery; the method realizes the ultra-fast synthesis of the high-performance sodium ion battery anode material with low energy consumption, and omits the high-temperature sintering process with high cost, time consumption and energy consumption in the traditional process; the preparation device and the process flow of the invention are simple, the product consistency is high, and the preparation device is suitable for large-scale macro preparation of the anode material powder.
Drawings
FIG. 1 is a schematic diagram of a Joule thermal sintering synthesis apparatus according to the present invention;
fig. 2 is a current variation curve recorded by the power module according to the first embodiment of the invention;
FIG. 3 is a temperature rise and fall curve recorded by the temperature measurement module according to the first embodiment of the present invention;
FIG. 4 is an X-ray diffraction pattern of a sodium vanadium fluorophosphate cathode material in the first embodiment of the present invention;
FIG. 5 is a scanning electron microscope image of the sodium vanadium fluorophosphate cathode material in the first embodiment of the present invention;
fig. 6 is a constant current charge and discharge curve of the sodium vanadium fluorophosphate cathode material in the first embodiment of the present invention.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
Example 1
1.82g of vanadium pentoxide (V) are taken 2 O 5 ) And 2.30g of ammonium dihydrogen phosphate (NH) 4 H 2 PO 4 ) Pouring the mixture into a ball milling tank, and mixing according to a ball material ratio of 1: adding 20 steel balls, adding a proper amount of absolute ethyl alcohol, performing high-energy ball milling for 24 hours, transferring the mixture to an oven after the ball milling is finished, fully drying at 80 ℃ to obtain powder, and dividing the powder into two parts, namely A and B.
Putting the powder A into a tube furnace, heating in the air at the speed of 5 ℃/min, preserving the heat for 4h when the temperature rises to 750 ℃, and then cooling to the room temperature along with the furnace to obtain a product of vanadyl phosphate (VOPO) 4 ) (ii) a Putting the powder B into a tube furnace, heating in argon-hydrogen mixed gas at the speed of 5 ℃/min, preserving heat for 5 hours when the temperature rises to 800 ℃, and then cooling to room temperature along with the furnace to obtain a product Vanadium Phosphate (VPO) 4 )。
1.29g VOPO were weighed out 4 、0.29g VPO 4 0.29g of sodium fluoride (NaF) and 0.42g of sodium carbonate (Na) 2 CO 3 ) Pouring the mixture into a ball milling tank, and mixing the materials according to a ball material ratio of 1: adding 20 steel balls, performing high-energy ball milling for 24 hours, transferring the mixture to an oven after the ball milling is finished, and fully drying at 80 ℃ to obtain precursor powder.
Cutting an electrochemical carbon cloth with the thickness of 0.5mm into a rectangle of 5 multiplied by 2cm, transferring the mixture subjected to ball milling to the carbon cloth in an argon atmosphere, connecting the carbon cloth and a power supply module into a passage through conductive copper adhesive, setting open-circuit voltage to be 20V, setting pulse current to be 13A and single pulse time to be 10s by adopting a rectangular wave signal, and taking out the carbon cloth and collecting a powder product after a program runs for a minimum period.
And adding the product into a beaker filled with 50mL of deionized water, fully stirring at the speed of 1000r/min for 12 hours, filtering after stirring, and placing the mixture into an oven for drying.
The active material was mixed with conductive carbon black (super P) and polyvinylidene fluoride (PVDF) according to 7:2:1 in N-methyl-2-pyrrolidone, evenly coated on a carbon-coated aluminum foil, and dried in an oven at 100 ℃ for 8 hours. Configuration of 1 MNaClO-containing 4 Dissolved in Ethylene Carbonate (EC): dimethyl carbonate (DMC): diethyl carbonate (DEC) =1:1: the solution 1 is used as electrolyte for electrochemical test, and a button cell is assembled to test electrochemical performance.
The current change curve and the temperature rise and fall curve in the process of preparing the sodium vanadium fluorophosphate material in the above embodiment are shown in fig. 2 and fig. 3, a rectangular wave signal is input into a circuit by a power supply module, the efficient and limited-range conversion of electric energy and heat energy is realized by an electrothermal conversion medium in a reactor, energy required by solid-phase reaction is provided for precursor powder, and a temperature measurement module displays that the joule heating sintering process has the characteristics of rapid temperature rise, short-time heat preservation and rapid cooling.
The X-ray diffraction pattern of the sodium vanadium fluorophosphate material prepared in the above example is shown in FIG. 4, which indicates that the synthesized substance is Na 3 (VO 0.8 PO 4 ) 2 F 1.4 Corresponding to JCPDS standard card # 98-1077. The scanning electron microscope image of the sodium vanadium fluorophosphate material prepared in the above example is shown in fig. 5, which shows that the synthesized material is in a lamellar morphology, the average particle size of the primary particles is 500nm, and the average particle size of the secondary particles is 1 μm. Fig. 6 shows a constant-current charge-discharge curve of the sodium vanadium fluorophosphate material prepared in the above embodiment, which indicates that the sodium vanadium fluorophosphate cathode material has two voltage platforms at 4.0V and 3.6V, respectively, and the 0.1C specific discharge capacity is 135mAh g -1 Reaching theoretical specific capacity, and the 1C specific discharge capacity is 122mAh g -1 And the theoretical specific capacity is 94.1 percent.
Example 2
Weighing 1.82g of vanadium pentoxide (V) 2 O 5 ) And 2.30g of ammonium dihydrogen phosphate (NH) 4 H 2 PO 4 ) Pouring the mixture into a ball milling tank, and mixing the materials according to a ball material ratio of 1:20 adding steel balls, then adding a proper amount of absolute ethyl alcohol, performing high-energy ball milling for 24 hours, and transferring the mixture to a baking oven after the ball milling is finishedThe cabinet was dried thoroughly at 80 ℃ to give a powder which was divided into two parts denoted A and B.
Putting the powder A into a tube furnace, heating in the air at the speed of 5 ℃/min, preserving heat for 4h when the temperature rises to 750 ℃, and then cooling to room temperature along with the furnace to obtain a product vanadyl phosphate (VOPO) 4 ) (ii) a Putting the powder B into a tube furnace, heating in argon-hydrogen mixed gas at the speed of 5 ℃/min, preserving the heat for 5 hours when the temperature rises to 800 ℃, and then cooling to the room temperature along with the furnace to obtain a product Vanadium Phosphate (VPO) 4 )。
1.29g VOPO were weighed out 4 、0.29g VPO 4 0.29g of sodium fluoride (NaF) and 0.42g of sodium carbonate (Na) 2 CO 3 ) Pouring the mixture into a ball milling tank, and mixing the materials according to a ball material ratio of 1: adding 20 steel balls, performing high-energy ball milling for 24 hours, transferring the mixture to an oven after the ball milling is finished, and fully drying at 80 ℃ to obtain precursor powder.
Cutting a nickel foil with the thickness of 0.02mm into a rectangle of 5 multiplied by 2cm, transferring the ball-milled mixture onto the nickel foil in an argon atmosphere, connecting the nickel foil and a power supply module into a passage through conductive copper adhesive, setting the open-circuit voltage to be 40V, setting the pulse current to be 44A and the single pulse time to be 30s by adopting a rectangular wave signal, and taking out the nickel foil and collecting a powder product after the program runs for a minimum period.
Adding the product into a beaker filled with 50mL of deionized water, fully stirring at the speed of 1000r/min for 12 hours, filtering after stirring, and placing the mixture into an oven for drying.
The active material was mixed with conductive carbon black (super P) and polyvinylidene fluoride (PVDF) according to 7:2:1 in the proportion of N-methyl-2-pyrrolidone, evenly coated on a carbon-coated aluminum foil, and dried in an oven at 100 ℃ for 8 hours. Configuration of 1 MNaClO-containing 4 Dissolved in Ethylene Carbonate (EC): dimethyl carbonate (DMC): diethyl carbonate (DEC) =1:1: the solution 1 is used as electrolyte for electrochemical test, and a button cell is assembled to test electrochemical performance.
Example 3
Weighing 1.82g of vanadium pentoxide (V) 2 O 5 ) And 2.30g of ammonium dihydrogen phosphate (NH) 4 H 2 PO 4 ) Pouring the mixture into a ball milling tank, and mixing the materials according to a ball material ratio of 1:20 adding steel ballsAnd then adding a proper amount of absolute ethyl alcohol, performing high-energy ball milling for 24 hours, transferring the mixture to an oven after the ball milling is finished, fully drying at 80 ℃ to obtain powder, and dividing the powder into two parts, namely A and B.
Putting the powder A into a tube furnace, heating in the air at the speed of 5 ℃/min, preserving heat for 4h when the temperature rises to 750 ℃, and then cooling to room temperature along with the furnace to obtain a product vanadyl phosphate (VOPO) 4 ) (ii) a Putting the powder B into a tube furnace, heating in argon-hydrogen mixed gas at the speed of 5 ℃/min, preserving the heat for 5 hours when the temperature rises to 800 ℃, and then cooling to the room temperature along with the furnace to obtain a product Vanadium Phosphate (VPO) 4 )。
1.29g VOPO were weighed out 4 、0.29g VPO 4 0.29g of sodium fluoride (NaF) and 0.42g of sodium carbonate (Na) 2 CO 3 ) Pouring the mixture into a ball milling tank, and mixing the materials according to a ball material ratio of 1: adding 20 steel balls, performing high-energy ball milling for 24 hours, transferring the mixture to an oven after the ball milling is finished, and fully drying at 80 ℃ to obtain precursor powder.
Cutting a cobalt foil with the thickness of 0.01mm into a rectangle of 6 multiplied by 2.5cm, transferring the ball-milled mixture onto the cobalt foil in an argon atmosphere, connecting the cobalt foil and a power supply module into a passage through conductive copper adhesive, setting an open-circuit voltage to be 36V, setting a pulse current to be 46A and a single pulse time to be 5s by adopting a rectangular wave signal, and taking out the cobalt foil and collecting a powder product after a program runs for a minimum period.
The product was added to a beaker containing 50mL of deionized water, stirred well at 1000r/min for 12h, and after stirring was complete, the mixture was placed in an oven to dry.
The active material was mixed with conductive carbon black (super P) and polyvinylidene fluoride (PVDF) according to 7:2:1 in the proportion of N-methyl-2-pyrrolidone, evenly coated on a carbon-coated aluminum foil, and dried in an oven at 100 ℃ for 8 hours. Preparation of 1M NaClO-containing 4 Dissolved in Ethylene Carbonate (EC): dimethyl carbonate (DMC): diethyl carbonate (DEC) =1:1: the solution 1 is used as electrolyte for electrochemical test, and a button cell is assembled to test electrochemical performance.
The preparation of the sodium vanadium fluorophosphate material can be realized by adjusting the process parameters according to the content of the invention, and the test shows that the performance is basically consistent with that of the invention. The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (10)
1. The method for synthesizing the sodium vanadium fluorophosphate by instantaneous Joule thermal sintering is characterized by comprising the following steps of: the chemical formula of the sodium vanadium fluorophosphate compound in the sodium vanadium fluorophosphate material is Na 3 (VO 1-x PO 4 ) 2 F 1+2x Wherein x is more than or equal to 0 and less than or equal to 1, the material has the shape characteristic of lamellar shape, the average grain diameter of primary particles in the material is 500nm, the average grain diameter of secondary particles in the material is 1 mu m, and the 0.1C specific discharge capacity of the material is 135mAh g -1 The specific 1C discharge capacity of the material is 122mAh g -1 And 94.1% of theoretical specific capacity can be achieved.
2. The method for preparing the material for synthesizing the sodium vanadium fluorophosphate by instantaneous joule heating sintering as claimed in claim 1, wherein the method comprises the following steps: the method comprises the following steps:
step 1, respectively placing a vanadium source, a phosphorus source, a fluorine source and a sodium source at room temperature of 15-35 ℃ for high-energy ball milling and then mixing, or mixing the vanadium source, the phosphorus source, the fluorine source and the sodium source and then placing at room temperature of 15-35 ℃ for high-energy ball milling to obtain a ball-milled mixture, wherein the stoichiometric ratio of the vanadium source to the phosphorus source to the fluorine source to the sodium source is 2, (0-3) to 3, excluding 0;
step 2, transferring the ball-milled mixture prepared in the step 1 to an electrothermal conversion medium in a reactor under an inert atmosphere, operating a function program of which the current and the voltage change along with time by using a joule heat sintering synthesis device, and collecting product powder from the reactor after the synthesis process is finished;
and 3, washing, filtering and drying the product powder prepared in the step 2 to obtain the sodium vanadium fluorophosphate material.
3. The preparation method of the instantaneous joule heating sintering synthesis of the sodium vanadium fluorophosphate material according to claim 2, which is characterized in that: in the step 1, one or more of vanadium pentoxide, ammonium metavanadate, vanadyl phosphate and vanadium phosphate is adopted as a vanadium source, one or more of diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphate, vanadyl phosphate and vanadium phosphate is adopted as a phosphorus source, one or more of sodium fluoride, sodium carbonate, sodium bicarbonate, sodium acetate and sodium oxalate is adopted as a sodium source, one or two of ammonium fluoride and sodium fluoride is adopted as a fluorine source, the stoichiometric ratio of the vanadium source to the phosphorus source to the fluorine source to the sodium source is 2.
4. The preparation method for synthesizing the sodium vanadium fluorophosphate material by instantaneous joule heating sintering according to claim 2, which is characterized by comprising the following steps of: in step 2, the joule heating sintering synthesizer comprises a power supply module, a reactor module and a temperature measuring module,
the power supply module is a direct-current programmable power supply, and regulates and controls the energy and temperature change of a load on an electrothermal conversion medium by programming a function program of current and voltage changing along with time, wherein the function program comprises one or more of sine waves, rectangular waves, sawtooth waves, triangular waves and step waves;
the reactor module comprises a conductive connecting piece and an electric-heat conversion medium, wherein the conductive connecting piece is used for fixing the electric-heat conversion medium and comprises one or more of conductive copper adhesive and conductive silver adhesive, the electric-heat conversion medium is used for realizing high-efficiency and limited-range conversion of electric energy and heat energy and providing energy required by solid-phase reaction for precursor powder and comprises one or more of carbon cloth, carbon felt, nickel foil, cobalt foil and iron foil;
the temperature measuring module is used for recording the temperature change along with the time in the reaction process, and adopts a non-contact temperature measuring device which comprises one or more of an infrared temperature measuring device, a laser temperature measuring device and a thermal imaging temperature measuring device;
the electric heating conversion medium is arranged on two sides of the electric heating conversion medium and connected with the power supply module through a lead, and the temperature measurement module is arranged above the electric heating conversion medium.
5. The preparation method of the instantaneous joule heating sintering synthesis of the sodium vanadium fluorophosphate material according to claim 2, which is characterized in that: in the step 2, one or more of argon, nitrogen and helium is adopted as inert atmosphere, preferably argon, when joule heating sintering synthesis reaction is carried out, the open circuit voltage of a power supply is 20-40V, the current is 10-50A, the reaction time is 2-60s, the electrothermal conversion medium adopts cobalt foil, nickel foil or electrochemical carbon cloth, and the electrothermal conversion medium adopts a rectangular structure with the thickness of 0.01-0.5mm (5-6) × (2-2.5) cm.
6. The preparation method of the instantaneous joule heating sintering synthesis of the sodium vanadium fluorophosphate material according to claim 2, which is characterized in that: in the step 3, the stirring speed in the water washing process is 500-1000r/min, the stirring time is 1-12h, the drying temperature is 40-100 ℃, preferably 60 ℃, and the drying time is 6-12h, preferably 12h.
7. The use of the instantaneous joule heating sintering synthesized sodium vanadium fluorophosphate material according to claim 1 in battery cathode materials.
8. A positive electrode material of a sodium-ion battery is characterized in that: the cathode material is made of the sodium vanadium fluorophosphate material prepared by the method in claim 1.
9. A battery positive electrode, characterized in that: the positive electrode is prepared by taking the positive electrode material of the sodium-ion battery as the raw material according to claim 8.
10. A battery, characterized by: the battery includes the battery positive electrode of claim 9.
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