CN110226252B - Polyanion type sodium ion battery positive electrode material and preparation method thereof - Google Patents
Polyanion type sodium ion battery positive electrode material and preparation method thereof Download PDFInfo
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- CN110226252B CN110226252B CN201880004520.6A CN201880004520A CN110226252B CN 110226252 B CN110226252 B CN 110226252B CN 201880004520 A CN201880004520 A CN 201880004520A CN 110226252 B CN110226252 B CN 110226252B
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- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 28
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229920000447 polyanionic polymer Polymers 0.000 title abstract description 9
- 239000011734 sodium Substances 0.000 claims abstract description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000011247 coating layer Substances 0.000 claims abstract description 6
- 239000013078 crystal Substances 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 38
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 35
- 239000002243 precursor Substances 0.000 claims description 32
- 239000000843 powder Substances 0.000 claims description 25
- 238000001354 calcination Methods 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 10
- 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 description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 239000003963 antioxidant agent Substances 0.000 claims description 7
- 230000003078 antioxidant effect Effects 0.000 claims description 7
- 235000006708 antioxidants Nutrition 0.000 claims description 7
- 239000002738 chelating agent Substances 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 229960005070 ascorbic acid Drugs 0.000 claims description 5
- 235000010323 ascorbic acid Nutrition 0.000 claims description 5
- 239000011668 ascorbic acid Substances 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 5
- 238000005303 weighing Methods 0.000 claims description 5
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical group [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 4
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000012703 sol-gel precursor Substances 0.000 claims description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- 239000011640 ferrous citrate Substances 0.000 claims description 3
- 235000019850 ferrous citrate Nutrition 0.000 claims description 3
- 229940062993 ferrous oxalate Drugs 0.000 claims description 3
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 claims description 3
- APVZWAOKZPNDNR-UHFFFAOYSA-L iron(ii) citrate Chemical compound [Fe+2].OC(=O)CC(O)(C([O-])=O)CC([O-])=O APVZWAOKZPNDNR-UHFFFAOYSA-L 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- 229940099259 vaseline Drugs 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000010405 anode material Substances 0.000 abstract description 11
- 239000010410 layer Substances 0.000 abstract description 4
- 230000003321 amplification Effects 0.000 abstract description 2
- 238000003199 nucleic acid amplification method Methods 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 230000002860 competitive effect Effects 0.000 abstract 1
- 239000012300 argon atmosphere Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 239000010406 cathode material Substances 0.000 description 7
- 239000002033 PVDF binder Substances 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 230000005469 synchrotron radiation Effects 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- 238000004729 solvothermal method Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229940040526 anhydrous sodium acetate Drugs 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to a polyanion type sodium ion battery anode material and a preparation method thereof. The polyanionic sodium-ion battery positive electrode material has the following chemical formula: na (Na) 4+2β Fe 3‑β (PO 4 ) 2 P 2 O 7 Wherein beta is more than or equal to 0 and less than or equal to 1/4, the polyanionic sodium-ion battery positive electrode material has an orthogonal crystal structure and belongs to Pn21a space group, and the thickness of the carbon coating layer is preferably 3-5nm. The battery anode material has good thermal stability and low cost of raw materials, is a new generation of competitive sodium ion battery anode material, and has the advantages of simple process flow, less equipment investment, high continuity degree, controllable cost, easy industrial amplification, uniform product particles, high purity and uniform carbon layer.
Description
Technical Field
The invention belongs to the field of positive electrode materials of sodium ion batteries, and particularly relates to a polyanion type positive electrode material of a sodium ion battery and a preparation method of the positive electrode material of the sodium ion battery.
Background
In recent years, global environmental problems have become more severe, and development of new renewable energy sources has been imminent. Lithium ion batteries, as the most promising sustainable energy, have been widely used in various fields such as portable mobile devices, electric vehicles, and energy storage, due to their advantages of high safety, high energy density, and long service life. However, the production and use costs are greatly affected by the global extreme maldistribution of lithium resources and the rapid mass consumption of lithium resources. Therefore, sodium ion batteries have been widely researched and paid attention to the global energy storage field due to their wide sodium resource distribution. The anode material is used as a key ring of the whole battery system, and indexes such as cycle stability, output voltage, thermal stability, output capacity, power density and the like of the anode material play decisive factors in the whole battery system.
At present, the main limiting factors of the polyanion type sodium ion battery anode material are lower electronic conductivity and higher ion transmission distance. Therefore, it is an effective means to coat the surface of the carbon layer with a nano carbon layer or to establish a two-dimensional and three-dimensional carbon skeleton network to improve the electronic conductivity. Meanwhile, aiming at large-scale industrial production, the existing preparation method of the polyanion type anode material mainly comprises a hydrothermal method, a solvothermal method, a high-temperature solid-phase method and the like. Wherein, the hydrothermal method has very complex process, and the cost of the organic solvent used by the solvothermal method is expensive; the energy consumption is large, the phase forming process is complex, and the intermediate process is uncontrollable; the high-temperature solid phase method has the problems of long calcination time, uneven mixing of raw materials, poor consistency and the like. The sol-gel method has simple process and low energy consumption, can mix precursor materials at an atomic level, and is a feasible preparation method capable of industrial large-scale production.
Therefore, there is an urgent need for a suitable high-rate positive electrode material with uniform carbon coating and with a nano-structure and a multi-dimensional carbon skeleton supporting structure.
Disclosure of Invention
The invention aims to provide a novel polyanion type sodium ion battery positive electrode material with adjustable morphology. Na of the invention 4+2β Fe 3-β (PO 4 ) 2 P 2 O 7 (beta is more than or equal to 0 and less than or equal to 1/4) material has a higher 3.2V discharge platform in the sodium-electricity anode material, and is close to 110mAh g -1 The lithium ion battery positive electrode material has the advantages of low price, easy obtainment, good thermal stability, stability in air, high power density and the like, and is a new generation of sodium battery positive electrode material with great prospect.
Specifically, the invention provides a polyanionic sodium-ion battery positive electrode material, which has the following chemical formula: na (Na) 4+2β Fe 3-β (PO 4 ) 2 P 2 O 7 Wherein beta is more than or equal to 0 and less than or equal to 1/4, the polyanionic sodium-ion battery positive electrode material has an orthogonal crystal structure and belongs to a Pn21a space group, and the polyanionic sodium-ion battery positive electrode material is provided with a carbon coating layer. The thickness of the carbon coating layer is preferably 3 to 5nm, and more preferably a uniform carbon coating layer of about 4 nm.
According to the polyanionic sodium-ion battery cathode material, when beta =0, the chemical formula of the material is Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 (ii) a When beta =1/4, the chemical formula of the material is Na 4.5 Fe 2.75 (PO 4 ) 2 P 2 O 7 (ii) a Within said range of beta values, na 4+2β Fe 3-β (PO 4 ) 2 P 2 O 7 The chemical formula of (beta is more than or equal to 0 and less than or equal to 1/4) is within the protection scope of the invention.
The material has the characteristics of high multiplying power and high power density, and a stable charging and discharging platform of about 3.2V, and has no attenuation of a median voltage after 430 cycles. And the device has the characteristics of controllable appearance and adjustable tap density, and can meet the requirements of different working conditions.
The second aspect of the invention provides a preparation method of a polyanionic sodium-ion battery anode material, which comprises the following steps:
A. preparation of the precursor
According to the chemical formula Na 4+2β Fe 3-β (PO 4 ) 2 P 2 O 7 Weighing a sodium source, an iron source and a phosphorus source in a metering manner, mixing the sodium source, the iron source and the phosphorus source with a carbon source, a chelating agent, an antioxidant and water, fully stirring and dissolving, and evaporating the obtained solution to dryness to obtain a uniformly dispersed sol-gel precursor; wherein beta is more than or equal to 0 and less than or equal to 1/4;
B. drying of the precursor
Under the protection of inert gas, drying the sol-gel precursor obtained in the step A to obtain precursor powder, and grinding the precursor powder;
C. calcination of precursor powder
And C, under the protection of inert gas, performing two-step temperature programming treatment on the precursor powder obtained in the step B: (1) The first step is that the temperature is programmed to 300-400 ℃, the precursor powder is cooled after being calcined, and the cooled precursor powder is ground for the second time; (2) And (3) continuously introducing inert gas for protection, carrying out programmed heating to 450-550 ℃ in the second step, and cooling after calcining to obtain the material.
According to the present invention, preferably, the sodium source is at least one of sodium acetate, sodium carbonate and sodium citrate.
According to the present invention, preferably, the iron source is at least one of ferrous acetate, ferrous oxalate and ferrous citrate.
According to the invention, preferably, the phosphorus source is ammonium monohydrogen phosphate and/or ammonium dihydrogen phosphate.
According to the present invention, preferably, the carbon source is at least one of vaseline, stearic acid, and sucrose; the adding amount of the carbon source is 5-20 wt% of the total mass of the solid raw materials.
According to the present invention, preferably, the chelating agent is citric acid and/or ethylenediaminetetraacetic acid; the addition amount of the chelating agent is 20-35 wt% of the total mass of the solid raw materials.
According to the invention, preferably, the antioxidant is ascorbic acid, and the addition amount of the antioxidant is 5-12 wt% of the total mass of the solid raw materials.
In the invention, the total mass of the solid raw materials refers to the total mass of a sodium source, an iron source, a phosphorus source, a carbon source, a chelating agent and an antioxidant.
According to the invention, the drying temperature is preferably 100-150 ℃ and the drying time is preferably 18-30h.
According to the invention, preferably, the temperature is raised to the calcination temperature at the speed of 1-3 ℃/min for the first time, and the calcination time is 8-15h; and the temperature is raised to the calcination temperature at the speed of 1-3 ℃/min for the second time, and the calcination time is 12-24h.
According to the present invention, preferably, the inert gas is argon.
The third aspect of the invention provides a positive electrode material for a sodium-ion battery obtained by the above-mentioned production method. It has the following chemical formula: na (Na) 4+2β Fe 3-β (PO 4 ) 2 P 2 O 7 Wherein beta is more than or equal to 0 and less than or equal to 1/4, has an orthogonal crystal structure and belongs to the Pn21a space group.
The invention has the following beneficial effects:
1. the invention provides a novel material of a high-power carbon-coated shape-controllable polyanion phosphate system for the field of positive electrode materials of sodium-ion batteries.
2. The high-power multilayer carbon-coated polyanionic sodium-ion battery positive electrode material Na 4+2β Fe 3-β (PO 4 ) 2 P 2 O 7 (beta is more than or equal to 0 and less than or equal to 1/4) has the characteristics of fine particle size (about 50-400 nm), uniform particle size distribution, uniform carbon layer and good product consistency.
3. The material of the invention has good thermal stability, excellent cycle performance, and higher discharge capacity and rate capability.
4. The material disclosed by the invention has better air stability and excellent low-temperature performance.
5. The material of the invention has higher stable charge-discharge platform (3.2V (vs. Na) + Na)), stable high power density can be provided.
6. The preparation method has the advantages of low calcination temperature, simple process and low production cost, and is beneficial to industrial production.
7. The preparation method is a one-step sol-gel method, and can construct a three-dimensional carbon network with controllable morphology. The method has the advantages of simple process flow, less equipment investment, high degree of continuity, controllable cost and easy industrial amplification.
8. The polyanionic sodium-ion electron anode material has excellent electrochemical performance, and the 0.05C discharge capacity is up to 113.0mAh g -1 Good multiplying power performance, 84.0mAh g under 20C multiplying power -1 The mass to capacity ratio of (d); the cycle performance is good, and the capacity retention rate of the capacitor is 84.0% and 69.1% after the capacitor is cycled for 430 times and 4400 times under the multiplying power of 0.5C and 20C. The material has good thermal stability and low raw material cost, and is a new generation of sodium ion battery anode material with high competitiveness.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The above and other objects, features and advantages of the present invention will become more apparent by describing in more detail exemplary embodiments thereof with reference to the attached drawings.
FIG. 1 is Na prepared in example 1 4 Fe 3 (PO 4 ) 2 P 2 O 7 And (3) a powder diffraction spectrogram and a fine modification result obtained by the synchrotron radiation X-ray source test of the material. The refinement is based on GSAS-II software.
FIG. 2 is Na prepared in example 2 4.5 Fe 2.75 (PO 4 ) 2 P 2 O 7 And (3) a powder diffraction spectrogram and a fine modification result obtained by the synchrotron radiation X-ray source test of the material. The refinement is also based on GSAS-II software.
FIG. 3 is a schematic view showing the result of refining the material obtained in example 1.
FIG. 4 is a graph showing the results of the finishing of the material obtained in example 2.
FIG. 5 is a scanning electron microscope photograph of the material obtained in example 1.
FIG. 6 shows a scanning electron microscope image of the material obtained in example 2 and carbon coating.
FIG. 7 is a scanning transmission electron microscope image of the material obtained in example 1 and the carbon coating.
FIG. 8 is the cycling stability at 0.05C current density for the material obtained in example 1.
FIG. 9 is a graph of 4400 cycles at 20C current for the material from example 1.
FIG. 10 is a graph of rate capability of the material obtained in example 2.
FIG. 11 is a transmission electron microscope and EDS energy spectrum of the material obtained in example 2 after cycling for 430 cycles at 0.5C discharge current.
FIG. 12 is a graph of the cycling stability of the material obtained in example 2 at 430 cycles at 0.5C.
FIG. 13 is a graph of a constant current batch titration of the material obtained in example 3.
FIG. 14 is a graph showing the discharge capacity of the first and second turns of the material obtained in example 3.
FIG. 15 is a CV diagram of the first five rings of the material obtained in example 3.
FIG. 16 is a graph of the stability of the material obtained in example 3 at a median voltage of 430 cycles.
Fig. 17A and 17B are graphs of magnetic properties of the material obtained in example 3.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein.
The invention is further illustrated by the following specific examples.
Example 1
In this embodiment, the preparation method comprises the following steps:
A. according to the chemical formula Na 4 Fe 3 (PO 4 ) 2 P 2 O 7 Weighing anhydrous sodium acetate 4mmol (analytically pure, purity)>99.5%) 0.3298g and anhydrous iron acetate 3mmol (analytically pure, pure)>99.0%) 0.5271g, stearic acid (analytically pure, pure)>99%) 0.1437g ascorbic acid (analytically pure, pure)>99%) 0.1286g, ammonium monohydrogen phosphate (analytically pure, pure)>99.5%) 0.5309g (4 mmol), ethylenediaminetetraacetic acid (analytically pure, pure)>99%) 0.8856g. Then 300mL of water was added to the flask and stirred at room temperature until dissolved, and then the flask was transferred to a 90 ℃ water bath and stirred until a semi-liquid gel was obtained.
B. Drying of precursor powder
And C, placing the gel material of the rheological phase obtained in the step A in a drying oven under the protection of argon atmosphere, and keeping the temperature at 120 ℃ for 24 hours. The xerogel obtained is then ground and pulverized.
C. Calcination of precursor powders
And D, placing the dried and crushed precursor powder in the step B into a tubular furnace, adding argon atmosphere for protection, heating to 350 ℃ by a first-step heating program of 2 ℃/min, calcining for 12h, cooling to room temperature, taking out the obtained precursor, and carrying out secondary grinding. And then placing the precursor into a tube furnace protected by argon atmosphere, heating to 450 ℃ by a second temperature rise program of 2 ℃/min, calcining for 24h, cooling to room temperature, and taking out the obtained final material.
The diffraction spectrum and the refinement result of the powder obtained by the synchrotron radiation X-ray source test of the material obtained in the embodiment are shown in figure 1. The specific occupancy information is shown in table 1. The result of the refinement is schematically shown in FIG. 3, and the morphology and carbon coating are shown in FIGS. 5 and 7.
And (3) testing the charge and discharge performance: the Na prepared in the embodiment is weighed according to the mass ratio of 80 4 Fe 3 (PO 4 ) 2 P 2 O 7 Adding the positive electrode material, acetylene black and polyvinylidene fluoride (PVDF) into a proper amount of N-methyl pyrrolidone to prepare slurry, and coating the slurry on an aluminum foil (the surface density is 2-3 mg cm) -2 ) Vacuum drying at 120 deg.C (vacuum degree of 0.094 MPa) for 12h, cutting into positive electrode sheet, and tabletting at 20 MPa. Takes a metal sodium sheet as a negative electrode, namely SIGMA-ALDRICHGlass fiber, manufactured by department of america, was used as a separator and was assembled into a button cell type CR2032 in an argon filled glove box. Electrochemical performance tests are performed in a voltage range of 1.9-4.1V, and the results show that the cathode material prepared in the embodiment has excellent electrochemical performance, and the electrochemical performance is 0.05C (1c = 120mag) -1 ) Can obtain 113.0mAh g at the current density of (2) -1 The capacity retention rate after 55 cycles of the discharge specific capacity (fig. 8) of (1) was close to 100%. Meanwhile, 80.3mAh g can still be obtained under the high discharge rate of 20C -1 The discharge specific capacity of (a) was determined, and the capacity retention rate was still 69.1% after 4400 cycles of cycling (fig. 9).
TABLE 1 refined Na by Rietveld 4 Fe 3 (PO 4 ) 2 P 2 O 7 Detailed structural information
Example 2
In this embodiment, the preparation method comprises the following steps:
A. according to the chemical formula Na 4.5 Fe 2.75 (PO 4 ) 2 P 2 O 7 Weighing 2.25mmol (analytically pure, purity) of anhydrous sodium carbonate>99.5%) 0.2397g and ferrous oxalate 2.75mmol (analytically pure, pure)>99.0%) 0.3998g vaseline (analytically pure, pure)>99%) 0.3g, ascorbic acid (analytically pure, pure)>99%) 0.2151g, ammonium dihydrogen phosphate (analytically pure, pure)>99.5%) 0.4625g (4 mmol), citric acid (analytically pure, pure)>99%) 0.5337g. Then 300mL of water was added to the flask and stirred at room temperature until dissolved, and then the flask was transferred to a 90 ℃ water bath and stirred until a semi-liquid gel was obtained.
B. Drying of precursor powder
And B, placing the rheological-phase gel material obtained in the step A in a drying oven under the protection of argon atmosphere, and keeping the temperature at 120 ℃ for 24 hours. The xerogel obtained is then ground and pulverized.
C. Calcination of precursor powders
And D, placing the dried and crushed precursor powder in the step B into a tubular furnace, adding argon atmosphere for protection, heating to 350 ℃ by a first-step heating program of 2 ℃/min, calcining for 12h, cooling to room temperature, taking out the obtained precursor, and carrying out secondary grinding. And then placing the precursor into a tube furnace protected by argon atmosphere, heating to 500 ℃ by a second temperature rise program of 2 ℃/min, calcining for 18h, cooling to room temperature, and taking out the obtained final material.
The diffraction spectrum and the refinement result of the powder obtained by the synchrotron radiation X-ray source test of the material obtained in the embodiment are shown in FIG. 2. The specific occupancy information is shown in table 2. The fine modification result is schematically shown in fig. 4, and the morphology and carbon coating are shown in fig. 6.
And (3) testing the charge and discharge performance: the Na prepared in the embodiment is weighed according to the mass ratio of 80 4.5 Fe 2.75 (PO 4 ) 2 P 2 O 7 Adding the positive electrode material, acetylene black and polyvinylidene fluoride (PVDF) into a proper amount of N-methyl pyrrolidone to prepare slurry, and coating the slurry on an aluminum foil (the surface density is 2-3 mg cm) -2 ) Vacuum drying at 120 deg.C (vacuum degree of 0.094 MPa) for 12h, cutting into positive electrode sheet, and tabletting at 20 MPa. A sodium metal sheet is taken as a negative electrode, glass fiber produced by SIGMA-ALDRICH company is taken as a diaphragm, and the diaphragm is assembled into a button cell with the model number of CR2032 in a glove box filled with argon. The electrochemical performance test is carried out within the voltage range of 1.9-4.1V, and the result shows that the cathode material prepared by the embodiment has excellent electrochemical performance. The magnification performance graph is shown in a transmission electron microscope and EDS energy spectrum graph of 10,0.5C after 430 cycles of discharge current circulation. These results indicate that the reaction is carried out over Na 4+2β Fe 3-β (PO 4 ) 2 P 2 O 7 Beta value range (beta is more than or equal to 0 and less than or equal to 1/4), and chemical formulas obtained at two ends of the beta value range have excellent electrochemical performance.
TABLE 2 refined Na by Rietveld 4.5 Fe 2.75 (PO 4 ) 2 P 2 O 7 Concrete structure letterInformation processing device
Example 3
In this embodiment, the preparation method comprises the following steps:
A. according to the chemical formula Na 4.25 Fe 2.875 (PO 4 ) 2 P 2 O 7 Weighing sodium citrate 1.4167mmol (analytically pure, purity)>99.5%) 0.3675g and ferrous citrate 0.9584mmol (analytically pure, pure)>99.0%) 0.5283g, sucrose (analytically pure, purity)>99%) 0.5g, ascorbic acid (analytically pure, pure)>99%) 0.2055g, ammonium monohydrogen phosphate (analytically pure, pure)>99.5%) 0.5309g (4 mmol), citric acid (analytically pure, pure)>99%) 0.5822g. Then 300mL of water was added to the flask and stirred at room temperature until dissolved, and then the flask was transferred to a 90 ℃ water bath and stirred until a semi-liquid gel was obtained.
B. Drying of precursor powder
And C, placing the gel material of the rheological phase obtained in the step A in a drying oven under the protection of argon atmosphere, and keeping the temperature at 120 ℃ for 24 hours. The xerogel obtained is then ground and pulverized.
C. Calcination of precursor powders
And D, placing the dried and crushed precursor powder in the step B into a tubular furnace, adding argon atmosphere for protection, heating to 350 ℃ by a first-step heating program of 2 ℃/min, calcining for 12h, cooling to room temperature, taking out the obtained precursor, and carrying out secondary grinding. And then placing the precursor into a tube furnace protected by argon atmosphere, heating to 550 ℃ by a second temperature rise program of 2 ℃/min, calcining for 12h, cooling to room temperature, and taking out the obtained final material.
And (3) testing charge and discharge performance: the Na prepared in the embodiment is weighed according to the mass ratio of 80 4.25 Fe 2.875 (PO 4 ) 2 P 2 O 7 Adding the positive electrode material, acetylene black and polyvinylidene fluoride (PVDF) into a proper amount of N-methyl pyrrolidone to prepare slurry, and coating the slurry on an aluminum foil (the surface density is 2-3 mg cm) -2 ) Vacuum drying at 120 deg.C (vacuum degree of 0.094 MPa) for 12h, cutting into positive electrode sheet, and tabletting at 20 MPa. A sodium metal sheet is taken as a negative electrode, glass fiber produced by SIGMA-ALDRICH company is taken as a diaphragm, and the diaphragm is assembled into a button cell with the model number of CR2032 in a glove box filled with argon. The electrochemical performance test is carried out in the voltage range of 1.9-4.1V, and the result shows that the cathode material prepared by the embodiment has excellent electrochemical performance. The current density of 0.5C is circulated for 430 times, and 84.0mAh g can still be obtained -1 Specific discharge capacity (fig. 12).
The results of the potentiostatic titration test obtained for this example are shown in FIG. 13. The first turn charge-discharge curve is shown in fig. 14. The first five cycles of the CV curve are shown in fig. 15. The median voltage stability after 430 cycles is shown in fig. 16. The magnetic test results are shown in fig. 17.
Within the chemical formula range of the cathode material, the materials obtained according to the specific embodiments have good electrochemical performance and cycle stability, and therefore, the polyanion type sodium ion battery cathode material is a sodium ion battery cathode material with high magnification and long service life and has a great prospect.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (9)
1. A preparation method of a polyanionic sodium-ion battery positive electrode material is characterized in that the polyanionic sodium-ion battery positive electrode material has the following chemical formula: na (Na) 4+2β Fe 3-β (PO 4 ) 2 P 2 O 7 Wherein beta is more than or equal to 1/8 and less than or equal to 1/4, the polyanionic sodium-ion battery has an orthogonal crystal structure and belongs to a Pn21a space groupThe positive electrode material is provided with a carbon coating layer, and the thickness of the carbon coating layer is 3-5nm;
the preparation method comprises the following steps:
A. preparation of the precursor
According to the chemical formula Na 4+2β Fe 3-β (PO 4 ) 2 P 2 O 7 Weighing a sodium source, an iron source and a phosphorus source in a metered manner, mixing the sodium source, the iron source and the phosphorus source with a carbon source, a chelating agent, an antioxidant and water, fully stirring and dissolving, and evaporating the obtained solution to dryness to obtain a uniformly dispersed sol-gel precursor;
B. drying the precursor
Under the protection of inert gas, drying the sol-gel precursor obtained in the step A to obtain precursor powder, and grinding the precursor powder;
C. calcination of precursor powder
And C, under the protection of inert gas, performing two-step temperature programming treatment on the precursor powder obtained in the step B: (1) The first step is that the temperature is programmed to 300-400 ℃, the precursor powder is cooled after being calcined, and the cooled precursor powder is ground for the second time; (2) And (3) continuously introducing inert gas for protection, carrying out programmed heating to 450-550 ℃ in the second step, and cooling after calcining to obtain the material.
2. The method of claim 1, wherein the sodium source is at least one of sodium acetate, sodium carbonate, and sodium citrate.
3. The method according to claim 1, wherein the iron source is at least one of ferrous acetate, ferrous oxalate and ferrous citrate.
4. The method of claim 1, wherein the phosphorus source is ammonium monohydrogen phosphate and/or ammonium dihydrogen phosphate.
5. The method of claim 1, wherein the carbon source is at least one of vaseline, stearic acid, and sucrose; the addition amount of the carbon source is 5-20 wt% of the total mass of the solid raw materials.
6. The method of claim 1, wherein the chelating agent is citric acid and/or ethylenediaminetetraacetic acid; the addition amount of the chelating agent is 20-35 wt% of the total mass of the solid raw materials.
7. The preparation method according to claim 1, wherein the antioxidant is ascorbic acid, and the addition amount of the antioxidant is 5 to 12wt% of the total mass of the solid raw materials.
8. The method according to claim 1, wherein the drying is carried out at a temperature of 100 to 150 ℃ for 18 to 30 hours; the calcination time after the first temperature programming is 8-15h, and the calcination time after the second temperature programming is 12-24 h; the inert gas is argon.
9. A polyanionic sodium-ion battery positive electrode material obtained by the production method according to any one of claims 1 to 8.
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| CN111446429B (en) * | 2020-03-27 | 2021-12-21 | 珠海冠宇电池股份有限公司 | Poly-polyanion cathode material and preparation method and application thereof |
| CN112768673B (en) * | 2021-02-04 | 2022-06-03 | 武汉大学 | Na4Fe3-x(PO4)2P2O7Positive electrode material of/C sodium ion battery and preparation method and application thereof |
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| CN113506865B (en) * | 2021-06-28 | 2024-03-22 | 山东玉皇新能源科技有限公司 | Battery negative electrode material and preparation method thereof |
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| CN116130624B (en) * | 2022-12-30 | 2023-12-01 | 浙江维思通新材料有限公司 | Preparation process of composite sodium ion battery anode material |
| CN116081591B (en) * | 2023-02-23 | 2024-05-14 | 武汉工程大学 | A method for preparing a negative electrode material for a sodium ion battery |
| CN116081594B (en) * | 2023-02-23 | 2024-07-09 | 武汉工程大学 | Preparation method of sodium ion battery anode material |
| CN116495717A (en) * | 2023-04-28 | 2023-07-28 | 多氟多新材料股份有限公司 | Preparation method of sodium ferrous fluorophosphate and preparation method of sodium ferrous fluorophosphate positive electrode material |
| CN116417598A (en) * | 2023-05-08 | 2023-07-11 | 广东工业大学 | Iron-based polyanion type sodium ion battery positive electrode material and preparation method thereof |
| CN116799200A (en) * | 2023-06-29 | 2023-09-22 | 宁波容百新能源科技股份有限公司 | A composite cathode material and its preparation method and application |
| CN116675207B (en) * | 2023-07-28 | 2023-10-20 | 赣州立探新能源科技有限公司 | Iron-based pyrophosphoric acid salt material, and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013163602A (en) * | 2012-02-09 | 2013-08-22 | National Institute Of Advanced Industrial Science & Technology | Iron-containing combined phosphate fluoride, its production method, and secondary battery using it as cathode active material |
| CN106784727A (en) * | 2017-01-17 | 2017-05-31 | 东莞市迈科新能源有限公司 | A kind of positive electrode material of polyanionic sodium ion battery and preparation method thereof |
| CN107069012A (en) * | 2017-04-24 | 2017-08-18 | 国网河南省电力公司电力科学研究院 | Hollow sphere Na4Fe3(PO4)2P2O7/ C composite anode materials and preparation method thereof |
| CN108046231A (en) * | 2017-11-13 | 2018-05-18 | 中南大学 | A kind of sodium-ion battery positive material and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101759323B1 (en) * | 2015-11-13 | 2017-07-18 | 주식회사 포스코 | Method for manufacturing cathod material of sodium rechargeable battery and sodium rechargeable battery including the same |
-
2018
- 2018-07-27 CN CN201880004520.6A patent/CN110226252B/en active Active
- 2018-07-27 WO PCT/CN2018/097471 patent/WO2020019311A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013163602A (en) * | 2012-02-09 | 2013-08-22 | National Institute Of Advanced Industrial Science & Technology | Iron-containing combined phosphate fluoride, its production method, and secondary battery using it as cathode active material |
| CN106784727A (en) * | 2017-01-17 | 2017-05-31 | 东莞市迈科新能源有限公司 | A kind of positive electrode material of polyanionic sodium ion battery and preparation method thereof |
| CN107069012A (en) * | 2017-04-24 | 2017-08-18 | 国网河南省电力公司电力科学研究院 | Hollow sphere Na4Fe3(PO4)2P2O7/ C composite anode materials and preparation method thereof |
| CN108046231A (en) * | 2017-11-13 | 2018-05-18 | 中南大学 | A kind of sodium-ion battery positive material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| Sol-gel synthesis of Na4Fe3(PO4)2(P2O7)/C nanocomposite for sodium ion batteries and new insights into microstructural evolution during sodium extraction;Xuehang Wu;《Journal of Power Sources》;20160930;1第667页右栏第2-3段、第668页右栏第2段 * |
| Xuehang Wu.Sol-gel synthesis of Na4Fe3(PO4)2(P2O7)/C nanocomposite for sodium ion batteries and new insights into microstructural evolution during sodium extraction.《Journal of Power Sources》.2016,666-674. * |
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