CN113745507A - Vanadium-oxygen-sodium chlorophosphate cathode material, preparation method and sodium ion battery - Google Patents
Vanadium-oxygen-sodium chlorophosphate cathode material, preparation method and sodium ion battery Download PDFInfo
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- CN113745507A CN113745507A CN202111026182.6A CN202111026182A CN113745507A CN 113745507 A CN113745507 A CN 113745507A CN 202111026182 A CN202111026182 A CN 202111026182A CN 113745507 A CN113745507 A CN 113745507A
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- 239000010406 cathode material Substances 0.000 title claims abstract description 30
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 16
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- -1 Vanadium-oxygen-sodium chlorophosphate Chemical compound 0.000 title description 21
- 239000011734 sodium Substances 0.000 claims abstract description 53
- 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 42
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 42
- ITVPBBDAZKBMRP-UHFFFAOYSA-N chloro-dioxido-oxo-$l^{5}-phosphane;hydron Chemical compound OP(O)(Cl)=O ITVPBBDAZKBMRP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 125000005287 vanadyl group Chemical group 0.000 claims abstract description 24
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000007774 positive electrode material Substances 0.000 claims abstract description 21
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 17
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 239000000460 chlorine Substances 0.000 claims description 22
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 13
- 229910052720 vanadium Inorganic materials 0.000 claims description 13
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 13
- 239000003792 electrolyte Substances 0.000 claims description 12
- 239000011780 sodium chloride Substances 0.000 claims description 11
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 9
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 9
- 239000011737 fluorine Substances 0.000 claims description 9
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 239000003365 glass fiber Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000005486 organic electrolyte Substances 0.000 claims description 8
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 8
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000000137 annealing Methods 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 229910003206 NH4VO3 Inorganic materials 0.000 claims description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 2
- 229910000352 vanadyl sulfate Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 98
- 238000003860 storage Methods 0.000 abstract description 21
- 239000013078 crystal Substances 0.000 abstract description 18
- 230000008569 process Effects 0.000 abstract description 9
- 150000001450 anions Chemical class 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 239000010405 anode material Substances 0.000 description 19
- 238000012360 testing method Methods 0.000 description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 239000002002 slurry Substances 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid group Chemical group C(C(=O)O)(=O)O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 230000001105 regulatory effect Effects 0.000 description 8
- 238000000576 coating method Methods 0.000 description 7
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 6
- 239000006230 acetylene black Substances 0.000 description 6
- 239000013543 active substance Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 235000010413 sodium alginate Nutrition 0.000 description 6
- 239000000661 sodium alginate Substances 0.000 description 6
- 229940005550 sodium alginate Drugs 0.000 description 6
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 6
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 6
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 229920000447 polyanionic polymer Polymers 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
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- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910017677 NH4H2 Inorganic materials 0.000 description 1
- 229910004565 Na2Fe2(SO4)3 Inorganic materials 0.000 description 1
- 229910020657 Na3V2(PO4)3 Inorganic materials 0.000 description 1
- 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 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
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- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
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- 230000009467 reduction Effects 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- 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
- C01B25/455—Phosphates containing halogen
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/582—Halogenides
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Abstract
本发明公开了一种氯磷酸钒氧钠正极材料、制备方法及钠离子电池，分子式为Na3(VO)2(PO4)2FxCly，空间群I4/mmm，属于四方晶系，所述Na3(VO)2(PO4)2FxCly为均匀规则立方体形状，通过对材料的阴离子位进行调控，采用一步水热方式成功的制备得到具有高储存稳定性、优异电化学性能和全天候性能表现的钠电正极材料通过调控阴离子方式，即调控F、Cl阴离子的比例，并调控水热温度制备钠离子电池正极材料，制备氯磷酸钒氧钠正极材料的具有更为优异的电化学性能，合成工艺方法简单，无需精密的仪器，适用于大规模生产。
The invention discloses a sodium vanadyl chlorophosphate positive electrode material, a preparation method and a sodium ion battery, the molecular formula is Na 3 (VO) 2 (PO 4 ) 2 F x C y , the space group is I4/mmm, and it belongs to the tetragonal crystal system. The Na 3 (VO) 2 (PO 4 ) 2 F x C y is in the shape of a uniform regular cube. By adjusting the anion site of the material, the one-step hydrothermal method is successfully prepared to obtain high storage stability and excellent electrochemical properties. The performance and all-weather performance of sodium-electric cathode materials are prepared by adjusting the anion method, that is, adjusting the ratio of F and Cl anions, and adjusting the hydrothermal temperature to prepare sodium-ion battery cathode materials, and the preparation of sodium vanadyl chlorophosphate cathode materials have better performance. Electrochemical performance, simple synthesis process, no need for sophisticated instruments, and suitable for large-scale production.
Description
Technical Field
The invention relates to the technical field of sodium-ion battery positive electrode materials, in particular to a vanadium-oxygen sodium chlorophosphate positive electrode material, a preparation method and a sodium-ion battery.
Background
In order to develop high-performance Sodium Ion Batteries (SIBs), advanced electrode materials are urgently required. Compared with the anode material, the cathode material is concerned more and the research is more mature. For example: hard carbon, alloy compounds, selenide and other negative electrode materials have been proved to have excellent sodium storage characteristics and future development prospects. Thus, the electrochemical performance of SIBs is to a large extent heavier than their cathode materials. In the research process of the anode material, the electrochemical performance of the material is more concerned: high multiplying power, long circulation, high energy density and wide temperature zone, and neglects the storage performance of the material. The storage properties of the materials are often of great significance in practical applications. It not only affects the electrochemical properties of the material, but also is very relevant to the cost of manufacturing the battery.
Most positive electrode materials are problematic in storage, and long-term exposure to air can cause the materials to absorb water and CO in the air2The reaction proceeds to impair the surface deactivation of the material and the reduction of the electrochemical properties.
Among the cathode materials, layered oxides and polyanion compounds are representative cathode materials with promising future practical prospects, and face huge storage challenges. O is3The type oxide is a relatively typical material among oxide materials, and has been widely studied and obtained satisfactory electrochemical properties. However, the O3 type oxide is less stable and reacts easily with water in the air. For example NaMO2And (M ═ Fe, Mn, Cr) materials, Na occurring when they come into contact with water+/H+Exchange reaction to form MOOH and NaOH, and CO in air2Reacting to form insulating Na2CO3And NaHCO3While sodium is allowed to diffuse to the surface of the material, inert particles are formed inside the material, resulting in deactivation of the entire electrode.
The polyanion compound is generally considered to be a more stable anode material, and has stronger covalent bond to stabilize oxygen in crystal lattice, so that the polyanion compound has higher structural stability and safety. In addition to having poor electronic conductivity, polyanionic compounds have another problem of havingThe surface of the material has strong water absorption, NaOH is generated when the surface of the material is contacted with water, and the electrochemical performance of the material is greatly influenced. Will react with CO in the air2Reaction to form insulating Na on the surface of the material2CO3And NaHCO3The electrochemical performance of the material is seriously influenced. For example Na2Fe2(SO4)3、Na3V2(PO4)3、Na4Fe2(PO4)2P2O7The polyanionic material has strong water absorption, and Na3TiV(PO4)3The structural stability is poor, and the Na can be generated by the spontaneous sodium removal action conversion after the sodium-free sodium salt is placed in the air for 30 days2TiV(PO4)3. Therefore, such materials are not suitable for long-term exposure to air, which presents a significant challenge to storage of the materials.
In conclusion, the poor storage stability of the material undoubtedly adds cost to the storage of the material, limiting the extent and the life of its use. And the research on the materials is very little and less, and the attention on the materials is far from the research on the electrochemical performance of the electrode materials. Therefore, development of a positive electrode material having excellent electrochemical performance and good storage stability is urgently required.
At present, the air stability of the material is usually solved by a coating method, and a layer of stable oxide, high molecular polymer and the like is coated on the surface of the material. However, these methods have high requirements on the process, which undoubtedly increase the production cost and also affect the electrochemical performance of the material, and the preparation of a sodium vanadium fluorophosphate/carbon composite and the application of the composite are disclosed in application numbers: 201711090279.7, a complex secondary carbon coating process is used. The carbon material will increase the mass of the material, reduce the mass/volume energy density of the whole material, affect the uniformity of the particle size of the material and have low repeatability.
Therefore, a simple hydrothermal mode is provided, and the sodium-electricity positive electrode material with high storage stability, excellent electrochemical performance and all-weather performance is successfully prepared by regulating and controlling the anion position of the material in one-step hydrothermal mode.
Disclosure of Invention
The invention aims to provide a sodium vanadyl chlorophosphate cathode material, a preparation method and a sodium ion battery, which have the advantages of low cost, excellent electrochemical performance, ultra-stable storage performance, good all-weather performance and wide application range.
In order to achieve the purpose, the invention provides the following technical scheme: vanadium-oxygen-sodium chlorophosphate cathode material with molecular formula of Na3(VO)2(PO4)2FxClyX + y is 1, 0.99 is more than or equal to x is more than or equal to 0.8, space group I4/mmm belongs to tetragonal system, and Na is3(VO)2(PO4)2FxClyIs in the shape of a uniform regular cube.
The preparation method of the sodium vanadyl chlorophosphate cathode material is characterized by comprising the following steps of:
s1: adding a vanadium source, a phosphorus source and a reducing agent into water, placing the mixture into a reaction container, heating and stirring the mixture at 70-80 ℃, wherein the stoichiometric ratio of vanadium in the vanadium source to water is 1:1-1: 10;
s2: adding a sodium source, a fluorine source and a chlorine source into the reaction container in the step S1, and reacting for 30-60min to obtain a uniform and transparent solution A; the stoichiometric ratio of fluorine in the fluorine source to chlorine in the chlorine source is 1:1 to 1: 7;
s3: adjusting the pH value of the transparent solution A prepared in the step S2 to 5-10, transferring the adjusted and controlled solution into a reaction kettle, heating to 100-200 ℃ for 6-36 hours;
s4: centrifuging, washing and drying the product obtained after the reaction in the step S3 to obtain a solid B;
s5: and (4) carrying out high-temperature annealing at 200-600 ℃ on the solid B prepared in the step S4 for 1-6 hours to obtain the sodium vanadyl chlorophosphate cathode material.
Preferably, the vanadium source is V2O5、NH4VO3 VOSO4One or more than two of them.
Preferably, the phosphorus source (NH)4)2HPO4、NH4H2PO4、H3PO4One or more than two of them.
Preferably, the sodium source is Na2CO3、NaHCO3、NaNO3And one or more than two of NaF, wherein the chlorine source is one or more than two of NaCl, HCl and hydroxylamine hydrochloride.
Preferably, the sodium source is NaF, the chlorine source is NaCl, and the ratio of NaF to NaCl is 1:3-1: 5. .
A sodium ion battery applying a sodium vanadyl chlorophosphate anode material comprises metal sodium serving as a cathode, glass fiber and electrolyte of a sodium ion battery to be tested, wherein the electrolyte is organic electrolyte and comprises 1M NaClO4Propylene carbonate and 5% by volume fluoroethylene carbonate.
Compared with the prior art, the invention has the beneficial effects that:
(1) na provided by the invention3V2(PO4)2O2FxThe Cy positive electrode material has a higher working voltage platform, a higher specific discharge capacity and a higher energy density, and has the characteristics of high initial discharge capacity, high working voltage, excellent all-weather performance and super-long storage stability; the material has good circulation stability, and the material still has the original structure, the original appearance and the original electrochemical stability after being placed for a period of time without treatment under the good water-oxygen condition, so that the storage cost of the material is undoubtedly reduced, and the application range of the material is widened.
(2) The invention relates to a preparation method of a sodium vanadyl chlorophosphate cathode material, which realizes modification of material crystal lattices by regulating an anion mode, namely regulating the proportion of F, Cl anions and regulating the proportion of F, Cl, changes the crystal growth direction of the material and leads the material to be along [010]]And (4) directionally growing. Obtaining the cathode material with uniform regular cube shape. Meanwhile, the electrochemical performance of the material is further optimized by adjusting F, Cl proportion. Adopts halogen ions to carry out double regulation and control on anion sites, not only modifies material crystal lattices, but also induces the crystal growth direction and widensSodium ion migration pathway (Cl)-With larger ionic radius) accelerates the kinetics of sodium ions in the de-intercalation process, improves the quick charge capacity of the material, stabilizes the crystal structure, improves the structural stability of the material, and ensures that the material has more excellent cycle performance.
(3) According to the invention, the crystal growth direction is changed by regulating and controlling F, Cl, so that the material has excellent air stability, the exposed [010] crystal face is more stable when the material is exposed and placed in air, and the material is not inactivated due to the formation of byproducts Na2CO3 and NaHCO3 by reaction with water and oxygen in the air, thereby having high air stability, providing convenience for storage of future materials, reducing the cost and prolonging the service life of the material. The hydrothermal temperature is regulated to prepare the material, and the crystallinity of the crystal and the particle size of the material can be changed by regulating the hydrothermal temperature, so that the overall electrochemical performance of the material, including the performances of multiplying power, circulation and the like, is influenced. The sodium ion battery anode material with good crystallinity, small material particle size and excellent electrochemical performance is obtained by regulating and controlling the hydrothermal temperature, has more excellent electrochemical performance, simple synthesis process method, no need of precise instruments and is suitable for large-scale production.
(4) The invention successfully prepares the high-performance anode material with uniform and controllable appearance by adopting a one-step hydrothermal carbon-coating-free mode, and omits a complex secondary carbon coating process. Meanwhile, the carbon-free material can reduce the material quality, improve the overall quality/volume energy density of the material and reduce the production cost. The material has uniform and controllable particle size, the repeatability of the material prepared each time can be ensured, and the process is more simple, convenient and mature. Meanwhile, compared with the prepared material, the prepared material has more excellent cycle performance and all-weather performance, the application environment field of the material is widened, and the market demand is met.
Drawings
FIG. 1 is an XRD characterization of the material prepared in example 1;
FIG. 2 is a SEM representation of the material prepared in example 1;
FIG. 3 is a XRD representation of the material after exposure to air for various periods of time;
figure 4 SEM characterization of the material after various times of exposure to air.
FIG. 5 is a graph of the rate performance of a material after being left in air for various periods of time;
FIG. 6 is a graph of low pressure test electrochemical performance;
FIG. 7 is a graph showing charge and discharge curves at different rates;
FIG. 8 is a 0.5C magnification cycle chart;
FIG. 9 is a graph of rate performance at different test temperatures.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Grinding the prepared positive electrode material, acetylene black and sodium carboxymethylcellulose or sodium alginate in a ratio of 7:2:1 and a solvent of deionized water to form slurry, uniformly coating the slurry on an aluminum foil, wherein the loading capacity of active substances of each electrode plate is 2-3mg/cm2. Using the electrolyte as a working electrode and a sodium sheet as a counter electrode, the electrolyte is respectively organic electrolyte 1M NaClO4+ propylene carbonate + 5% by volume of fluoroethylene carbonate. The septum is glass fiber (Whatman 934-AH). After the cell was assembled in a glove box in an oxygen-free and water-free argon environment, constant current charge and discharge tests were performed on LAND.
Basic embodiment
S1: adding a vanadium source, a phosphorus source and a reducing agent into water, placing the mixture into a reaction container, heating and stirring the mixture at 70-80 ℃, wherein the stoichiometric ratio of vanadium in the vanadium source to water is 1:1-1: 10; the reducing agent is oxalic acid;
s2: adding a sodium source, a fluorine source and a chlorine source into the reaction container in the step S1, and reacting for 30-60min to obtain a uniform and transparent solution A; the stoichiometric ratio of fluorine in the fluorine source to chlorine in the chlorine source is 1:1 to 1: 9;
s3: adjusting the pH value of the transparent solution A prepared in the step S2 to 5-10, transferring the adjusted and controlled solution into a reaction kettle, heating to 100-200 ℃ for 6-36 hours;
s4: centrifuging, washing and drying the product obtained after the reaction in the step S3 to obtain a solid B;
s5: and (4) carrying out high-temperature annealing at 200-600 ℃ on the solid B prepared in the step S4 for 1-6 hours to obtain the sodium vanadyl chlorophosphate cathode material.
Example one
S1: will V2O5Oxalic acid, NH4H2PO4Adding to water, V2O5: oxalic acid: NH (NH)4H2PO4In a molar ratio of 1: 3: 2, V2O5The molar ratio of vanadium to water in the vanadium-containing catalyst is 1-10; heating and stirring the mixture for 1 hour at 80 ℃ in a reaction vessel;
s2: adding NaF and NaCl into the reaction container in the step S1 according to the ratio of 1:3, and reacting for 45min to obtain a uniform and transparent solution A;
s3: adjusting the pH value of the transparent solution A prepared in the step S2 to 7, transferring the adjusted solution into a reaction kettle, heating the solution in an oven at 170 ℃ for 12 hours;
s4: washing the product obtained after the reaction in the step S3 by centrifugation, and drying the product in an oven at 100 ℃ to obtain a solid B;
s5: and (4) annealing the solid B prepared in the step S4 at the high temperature of 400 ℃ for 4 hours to obtain the sodium vanadyl chlorophosphate cathode material.
Examples two to six
The process steps are the same as in example 1 except that in step S3 the pH values are 6, 8, 9 and 10, respectively.
Comparative examples one to six
The method steps are the same as the first embodiment, except that the pH values in the step S3 are 2-5 and 11-12 respectively.
Specific discharge capacity of the vanadium oxygen sodium chlorophosphate positive electrode materials prepared by implementing the first to sixth and the first to sixth comparative examples is tested, and is shown in table 1.
TABLE 1
As can be seen from Table 1, the specific discharge capacity of the prepared sodium vanadyl chlorophosphate cathode material is 115mAh g when the pH is adjusted to 6-10-1Above, wherein at pH 7, the optimum specific discharge capacity was exhibited at 127mAh g-1In the preparation process, the pH value not only influences the performance of the material, but also further influences the appearance and crystallinity of the material in the nucleation process. When the pH value of the material is less than 6, the whole solution of the solution is relatively strong in acidity, and can corrode the material in the nucleation process of the material, so that the morphology of the material is influenced, the crystallinity of the material is reduced, the particle size of the material is relatively large, the shape of the material is irregular, and meanwhile, the stability of the crystal structure of the material is influenced by the relatively poor crystallinity, and the overall performance of the material is relatively poor. The influence of pH adjustment in the reaction process is analyzed in depth, so that the vanadium-oxygen-sodium chlorophosphate cathode material prepared at the pH of 6-10 shows excellent specific discharge capacity.
Examples seven to nine
The method steps are the same as the first embodiment, except that the ratios of NaF to NaCl in the step S2 are 1:1, 1:5 and 1:7 respectively.
Comparative example seven
The method steps are the same as in example one, except that the ratio of NaF to NaCl in step S2 is 1:9, respectively.
The specific discharge capacity of the vanadium-oxygen-sodium chlorophosphate anode materials prepared by the first, seventh to ninth embodiments and the seventh comparative example is tested, and is shown in table 2.
TABLE 2
As can be seen from Table 2, the ratio of NaF to NaCl is in the range of 1:1 to 1:7, and the prepared sodium vanadyl chlorophosphate cathode material has excellent specific discharge capacity, whereinWhen the ratio of NaF to NaCl is 1:3, the optimal specific discharge capacity is 127mAh g-1。
And (3) performance testing:
(1) storage stability test
Respectively exposing the vanadium sodium oxygen chlorophosphate positive electrode material prepared in the first embodiment to air, standing for 1-36 months, grinding the exposed material, acetylene black, sodium carboxymethylcellulose or sodium alginate in a ratio of 7:2:1 and a solvent of deionized water to form slurry, and uniformly coating the slurry on an aluminum foil, wherein the loading capacity of active substances of each electrode plate is 2-3mg/cm 2. The working electrode was a sodium sheet, and the electrolyte was an organic electrolyte of 1M NaClO4+ propylene carbonate + fluoroethylene carbonate of 5% by volume. The septum is glass fiber (Whatman 934-AH). After the cell was assembled in a glove box in an oxygen-free and water-free argon environment, constant current charge and discharge tests were performed on LAND. The test structure is shown in table 3.
TABLE 3
(2) Stability testing at different storage temperatures
Respectively exposing the vanadium sodium oxygen chlorophosphate positive electrode material prepared in the first embodiment, placing the exposed vanadium sodium oxygen chlorophosphate positive electrode material in different temperature ranges for 24 hours, grinding the exposed material, acetylene black, sodium carboxymethylcellulose or sodium alginate in a ratio of 7:2:1 and a solvent of deionized water to form slurry, and uniformly coating the slurry on an aluminum foil (the loading amount of active substances of each electrode plate is 2-3 mg/cm)2). Using the electrolyte as a working electrode and a sodium sheet as a counter electrode, the electrolyte is respectively organic electrolyte 1M NaClO4+ propylene carbonate + 5% by volume of fluoroethylene carbonate. The septum is glass fiber (Whatman 934-AH). After the cell was assembled in a glove box in an oxygen-free and water-free argon environment, constant current charge and discharge tests were performed on LAND. The test results are shown in table 4.
TABLE 4
(3) Test of storage stability in water environment
Exposing the vanadium sodium oxygen chlorophosphate positive electrode material prepared in the first embodiment, placing the vanadium sodium oxygen chlorophosphate positive electrode material in water for different time periods, grinding the material dried by the material, acetylene black, sodium carboxymethylcellulose or sodium alginate in a ratio of 7:2:1 and a solvent of deionized water to form slurry, and uniformly coating the slurry on an aluminum foil (the loading amount of active substances of each electrode plate is 2-3mg/cm 2). The working electrode was a sodium sheet, and the electrolyte was an organic electrolyte of 1M NaClO4+ propylene carbonate + fluoroethylene carbonate of 5% by volume. The septum is glass fiber (Whatman 934-AH). After the cell was assembled in a glove box in an oxygen-free and water-free argon environment, constant current charge and discharge tests were performed on LAND. The test results are shown in table 5.
TABLE 5
As can be seen from tables 3-5, the vanadium-oxygen-sodium chlorophosphate anode material prepared by the method disclosed by the invention is basically stable in specific discharge capacity and does not have obvious change when exposed to air for a long time in environments of different temperatures, water environments and the like, and the vanadium-oxygen-sodium chlorophosphate anode material prepared by the method disclosed by the invention has better stability and is suitable for all weather.
(4) All weather performance test
The vanadium sodium oxygen chlorophosphate anode material prepared in the first embodiment is dried, the dried vanadium sodium oxygen chlorophosphate anode material, acetylene black, sodium carboxymethylcellulose or sodium alginate are ground into slurry according to the proportion of 7:2:1 and the solvent is deionized water, and the slurry is uniformly coated on an aluminum foil (the loading amount of active substances of each electrode plate is 2-3mg/cm 2). The working electrode was a sodium sheet, and the electrolyte was an organic electrolyte of 1M NaClO4+ propylene carbonate + fluoroethylene carbonate of 5% by volume. The septum is glass fiber (Whatman 934-AH). After assembling the battery in an argon oxygen-free and water-free environment of a glove box, carrying out constant-current charge and discharge test on LAND, modulating the voltage measuring range by 1.2-4.3V, and testing the wide voltage range performance of the battery.
(5) All weather performance test
The vanadium sodium oxygen chlorophosphate anode material prepared in the first embodiment is dried, the dried vanadium sodium oxygen chlorophosphate anode material, acetylene black, sodium carboxymethylcellulose or sodium alginate are ground into slurry according to the proportion of 7:2:1 and the solvent is deionized water, and the slurry is uniformly coated on an aluminum foil (the loading amount of active substances of each electrode plate is 2-3mg/cm 2). The working electrode was a sodium sheet, and the electrolyte was an organic electrolyte of 1M NaClO4+ propylene carbonate + fluoroethylene carbonate of 5% by volume. The septum is glass fiber (Whatman 934-AH). After the cell was assembled in a glove box in an oxygen-free and water-free argon environment, constant current charge and discharge tests were performed on LAND. And testing the all-weather performance of the electrical measurement. The test results are shown in table 6.
TABLE 6
Fig. 1 is an XRD characterization pattern of the material prepared in example 1, and XRD characterization data shows that the sodium vanadyl chlorophosphate cathode material successfully prepared does not have any impurity and exhibits good crystallinity.
FIG. 2 is an SEM representation of the material prepared in example 1, wherein the sodium vanadyl chlorophosphate anode material has a cubic block shape with regular micron size, the particle size is about 1.5um, and the uniform particle size and regular shape are beneficial to the exertion of material performance.
FIG. 3 is an XRD representation diagram of the material after being placed in the air for different times, and FIG. 4 is an SEM representation diagram of the material after being placed in the air for different times, and the results show that no matter what conditions are under which the crystal structure of the sodium vanadyl chlorophosphate positive electrode material is changed, the good crystallinity is shown, and no impurity phase exists; the result shows that the sodium vanadyl chlorophosphate cathode material has good storage stability.
FIG. 5 is a graph of the rate performance of a material after being left in air for various periods of time; the result shows that no matter what kind of conditions are used for placing, the initial capacity and the rate performance of the sodium vanadyl chlorophosphate anode material do not have large fluctuation, and the anode material has excellent electrochemical performance; indicating that NVPFCl has good storage stability.
FIG. 6 is a graph of low voltage electrochemical performance showing higher specific discharge capacity (172mAh g) for rate capability over a wider voltage range-1) And excellent rate performance. Proves that the sodium vanadyl chlorophosphate cathode material has excellent electrochemical performance.
FIG. 7 is a charge-discharge curve diagram under different multiplying powers, constant-current charge-discharge curve tests are carried out in a wider voltage interval, the sodium vanadyl chlorophosphate anode material shows that three discharge platforms are respectively 4.0V, 3.6V and 1.5V under the low multiplying power, and the high specific discharge capacity is 172mAh g-1。
FIG. 8 is a 0.5C magnification cycle chart; the capacity retention rate of 86.8 percent is still maintained after 100 cycles of circulation under the current density of 0.5C, and the result proves that the sodium vanadyl chlorophosphate cathode material has excellent structural stability and good cycle life performance.
FIG. 9 is a graph of rate capability at different test temperatures, and the sodium vanadyl chlorophosphate cathode material has excellent rate performance when the temperature is increased by 50 degrees, and 116mAh g is still remained even at 20C-1Exhibits excellent high temperature performance. Meanwhile, the sodium vanadyl chlorophosphate anode material still has good rate performance at the temperature of 15 ℃, and the performance is almost the same as that at room temperature. The result shows that the sodium vanadyl chlorophosphate anode material shows excellent temperature adaptation, can be matched with different temperature measurement intervals, and can provide greater convenience for future application.
In summary, the analysis in tables 1 to 4 and fig. 1 to 9 is combined, the modification of the material lattice is realized by adjusting the proportion of F, Cl, the crystal growth direction of the material is changed, and the material is grown along the [010] direction. Obtaining the cathode material with uniform regular cube shape. Meanwhile, the electrochemical performance of the material is further optimized by adjusting F, Cl proportion. The halogen ions are adopted to carry out double regulation and control on the anion position, not only are the material crystal lattices modified, but also the crystal growth direction is induced, the sodium ion migration path is widened, namely Cl < - > has larger ionic radius, the kinetics of the sodium ions in the de-intercalation process are accelerated, the quick charge capacity of the material is improved, the crystal structure is stabilized, the structural stability of the material is improved, and the material has more excellent cycle performance.
In addition, it can be seen from tables 5-6 that the vanadium oxygen sodium chlorophosphate cathode material prepared by the present invention still maintains superior specific discharge capacity after long-term exposure in air and in water, since the crystal growth direction is changed by controlling F, Cl, the material has superior air stability, and the exposed [010] is exposed after air exposure]The crystal face is more stable and can not react with water and oxygen in the air to form a by-product Na2CO3And NaHCO3Resulting in deactivation of the material and thus high air stability, which also facilitates storage of the material in the future, reduces its cost and increases its lifetime.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (7)
1. The sodium vanadyl chlorophosphate cathode material is characterized in that the molecular formula is Na3(VO)2(PO4)2FxClyX + y is 1, 0.99 is more than or equal to x is more than or equal to 0.8, space group I4/mmm belongs to tetragonal system, and Na is3(VO)2(PO4)2FxClyIs in the shape of a uniform regular cube.
2. The preparation method of the cathode material according to claim 1, wherein the preparation method is carried out in a one-step hydrothermal manner, and comprises the following specific steps:
s1: adding a vanadium source, a phosphorus source and a reducing agent into water, placing the mixture into a reaction container, heating and stirring the mixture at 70-80 ℃, wherein the stoichiometric ratio of vanadium in the vanadium source to water is 1:1-1: 10;
s2: adding a sodium source, a fluorine source and a chlorine source into the reaction container in the step S1, and reacting for 30-60min to obtain a uniform and transparent solution A; the stoichiometric ratio of fluorine in the fluorine source to chlorine in the chlorine source is 1:1 to 1: 7;
s3: adjusting the pH value of the transparent solution A prepared in the step S2 to 6-10, transferring the adjusted and controlled solution into a reaction kettle, heating to 100-200 ℃ for 6-36 hours;
s4: centrifuging, washing and drying the product obtained after the reaction in the step S3 to obtain a solid B;
s5: and (4) carrying out high-temperature annealing at 200-600 ℃ on the solid B prepared in the step S4 for 1-6 hours to obtain the sodium vanadyl chlorophosphate cathode material.
3. The method for producing a positive electrode material according to claim 2, wherein the vanadium source is V2O5、NH4VO3VOSO4One or more than two of them.
4. The method for preparing the positive electrode material according to claim 2, wherein the phosphorus source (NH)4)2HPO4、NH4H2PO4、H3PO4One or more than two of them.
5. The method for producing a positive electrode material according to claim 2, wherein the positive electrode material is produced by a method comprisingThe sodium source is Na2CO3、NaHCO3、NaNO3And one or more than two of NaF, wherein the chlorine source is one or more than two of NaCl, HCl and hydroxylamine hydrochloride.
6. The method for preparing the positive electrode material according to claim 5, wherein the sodium source is NaF, the chlorine source is NaCl, and the ratio of NaF to NaCl is 1:3 to 1:5, respectively.
7. The sodium ion battery using the positive electrode material as claimed in claim 1, comprising metal sodium as a negative electrode, glass fiber, and an electrolyte of a sodium ion battery to be tested, wherein the electrolyte is an organic electrolyte comprising NaClO4Propylene carbonate and 5% by volume fluoroethylene carbonate.
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