CN111261857B - FePS for sodium ion battery3/NC composite negative electrode material, preparation method thereof and sodium ion battery - Google Patents
FePS for sodium ion battery3/NC composite negative electrode material, preparation method thereof and sodium ion battery Download PDFInfo
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- CN111261857B CN111261857B CN202010068818.2A CN202010068818A CN111261857B CN 111261857 B CN111261857 B CN 111261857B CN 202010068818 A CN202010068818 A CN 202010068818A CN 111261857 B CN111261857 B CN 111261857B
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 86
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000002131 composite material Substances 0.000 title claims abstract description 68
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229910005318 FePS3 Inorganic materials 0.000 claims abstract description 71
- 239000000463 material Substances 0.000 claims abstract description 46
- 239000012298 atmosphere Substances 0.000 claims abstract description 23
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229960001149 dopamine hydrochloride Drugs 0.000 claims abstract description 13
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 10
- 239000007983 Tris buffer Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000012670 alkaline solution Substances 0.000 claims abstract description 6
- 238000004321 preservation Methods 0.000 claims abstract description 6
- 239000007788 liquid Substances 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 239000013078 crystal Substances 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 20
- 239000003792 electrolyte Substances 0.000 claims description 19
- 238000005245 sintering Methods 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- 239000011889 copper foil Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 239000011259 mixed solution Substances 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000004108 freeze drying Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000000527 sonication Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 239000010405 anode material Substances 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 14
- 239000002135 nanosheet Substances 0.000 description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 11
- 229910052708 sodium Inorganic materials 0.000 description 11
- 239000011734 sodium Substances 0.000 description 11
- -1 transition metal phosphosulfide Chemical class 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 239000006258 conductive agent Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 239000012300 argon atmosphere Substances 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical group [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 6
- 238000000137 annealing Methods 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 description 6
- 239000012528 membrane Substances 0.000 description 6
- 239000002109 single walled nanotube Substances 0.000 description 6
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 6
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000010406 cathode material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000003365 glass fiber Substances 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000006713 insertion reaction Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
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- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- 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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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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Abstract
The invention relates to FePS for a sodium ion battery3A/NC composite negative electrode material, a preparation method thereof and a sodium ion battery belong to the technical field of sodium ion batteries. The FePS for the sodium ion battery of the invention3The preparation method of the/NC composite anode material comprises the following steps: FePS is prepared3Adding dopamine hydrochloride into alkaline solution, stirring for 12-48h, and carrying out solid-liquid separation to obtain FePS3@ PDA material; the alkaline solution is a Tris buffer solution; the prepared FePS3The @ PDA material is subjected to heat preservation for 1-5h at 800 ℃ in a reducing atmosphere or an inert atmosphere to obtain the material. The FePS for the sodium ion battery of the invention3The sodium ion battery made of the/NC composite negative electrode material has high discharge capacity, long cycle life and excellent rate performance, discharges at 5A/g, and has the capacity about 300 mAh/g.
Description
Technical Field
The invention relates to FePS for a sodium ion battery3A/NC composite negative electrode material, a preparation method thereof and a sodium ion battery belong to the technical field of sodium ion batteries.
Background
Lithium ion batteries are currently the most mature energy storage devices due to their excellent electrochemical properties, and are widely used in small-sized portable electronic devices, large-sized devices such as electric vehicles, and the like. With the rapid growth of the electric automobile industry in recent years, the demand of lithium ion batteries is increasing, but the lithium resources in nature are relatively deficient, and the shortage of lithium sources and the increase of production cost limit the long-term development and utilization of lithium ion batteries, so that the demand of large-scale application cannot be met.
The sodium ion battery is similar to the lithium ion battery in terms of an energy storage mechanism, the content of metal sodium in the earth crust is rich, the electrode potential of the metal sodium is lower than that of the metal lithium, and the selectivity of the metal sodium to electrolyte is higher. The sodium ion battery has relatively stable electrochemical performance and is safer to use.
The commonly used sodium ion battery cathode materials at present mainly comprise hard carbon materials, alloy materials, nonmetal simple substances, metal compounds and the like. The radius of the sodium ions is large, so that the difficulty of the sodium ions in the electrode material in the process of charge and discharge is increased, and the current sodium ion battery cathode material is difficult to exert high specific capacity and long cycle life.
Disclosure of Invention
The invention provides FePS for a sodium ion battery3A preparation method of a/NC composite negative electrode material aims to solve the problems of low specific capacity and short cycle life of a negative electrode material of a sodium-ion battery in the prior art.
The invention also provides FePS for the sodium ion battery prepared by the preparation method3The patent refers to the field of 'processes or means for the direct conversion of chemical energy into electrical energy'.
The technical scheme adopted by the invention for solving the technical problems is as follows:
FePS for sodium ion battery3The preparation method of the/NC composite anode material comprises the following steps:
1) FePS is prepared3Adding dopamine hydrochloride into alkaline solution, stirring for 12-48h, and carrying out solid-liquid separation to obtain FePS3@ PDA material; the alkaline solution is a Tris buffer solution;
2) FePS prepared in the step 1)3The @ PDA material is subjected to heat preservation for 1-5h at 800 ℃ in a reducing atmosphere or an inert atmosphere to obtain the material.
The FePS3The mass ratio of the dopamine hydrochloride to the dopamine hydrochloride is 1-5: 1.
Washing and vacuum drying the solid obtained after solid-liquid separation in the step 1); the washing is that the washing is firstly carried out for more than 3 times by using deionized water, and then the washing is carried out for more than three times by using absolute ethyl alcohol. The temperature of the vacuum drying is 50-80 ℃, and the time of the vacuum drying is 12-48 h.
In the step 2), the reducing atmosphere is hydrogen or a mixed gas of hydrogen and argon. The inert atmosphere in the step 2) is argon or nitrogen.
Preferably, the FePS3Is FePS3Nanosheets.
The FePS3Is prepared by the method comprising the following steps:
a) uniformly grinding iron powder, phosphorus powder and sulfur powder, and then sintering in vacuum at 600-800 ℃ for 3-6d to obtain block FePS3A crystal;
b) the block FePS prepared in the step a) is3Calcining the crystal for 2-10h at the temperature of 300-700 ℃ under the inert atmosphere;
c) uniformly mixing the calcined material obtained in the step b) with water to obtain a mixed solution, carrying out ultrasonic treatment on the mixed solution for 5-10 hours, and carrying out freeze drying.
The phosphorus powder in the step a) is red phosphorus powder. The sulfur powder in the step a) is sublimed sulfur powder.
The molar ratio of the iron powder to the phosphorus powder to the sulfur powder in the step a) is 1:1: 3-5.
The vacuum degree of the vacuum sintering in the step a) is 10-6 mbar.
The inert atmosphere in step b) is nitrogen or argon.
In step b) the bulk FePS is reacted under an inert gas atmosphere3The temperature of the crystal is raised to 300-700 ℃ at the speed of 1-10 ℃/min.
The temperature of the freeze-drying in step c) is-50-0 ℃.
The sonication in step c) is carried out under ice bath conditions.
The ratio of calcined material to water in step c) is 100mg of calcined material to 50-200mL of water.
FePS for sodium ion battery prepared by preparation method3the/NC composite negative electrode material.
A sodium ion battery comprises a positive electrode, a negative electrode, a diaphragm and electrolyte, wherein the negative electrode comprises a negative current collector copper foil and a negative electrode material layer coated on the surface of the negative current collector, the negative electrode material layer comprises a negative active substance, a conductive agent and a binder, and the negative active substance is the FePS3the/NC composite negative electrode material.
The invention has the beneficial effects that:
the FePS for the sodium ion battery of the invention3Laminated structure of/NC composite anode materialCarbon is uniformly attached to the surface. Wherein, FePS3Is ternary transition metal phosphosulfide and has special two-dimensional layered structure with van der waals force combination between layers, and this structure is favorable to the fast motion and storage of sodium ion between layers. The conversion reaction mechanism is different from the traditional insertion reaction and alloying reaction, and when the material is used as a negative electrode material of a sodium ion battery, the theoretical capacity exceeds 1300 mAh/g. However, FePS3In the process of charging and discharging, the material can cause serious volume expansion due to intercalation and deintercalation of sodium ions, so that capacity is attenuated, the stability of the material is greatly reduced, and the cycle performance of the material is influenced. FePS of the invention3the/NC composite cathode material is in FePS3The coating effectively buffers the volume expansion of the material in the reaction process and promotes the rapid transfer of electrons/ions. Can realize longer cycle life on the premise of keeping higher specific capacity.
In addition, the rate performance of the material is greatly enhanced by improving the stability of the material system, and the FePS for the sodium ion battery provided by the invention3The sodium ion battery made of the/NC composite negative electrode material has high discharge capacity and excellent rate capability, discharges at 5A/g, and has the capacity about 300 mAh/g.
Drawings
FIG. 1 shows FePS for sodium ion battery in example 13SEM image of/NC composite cathode material;
FIG. 2 shows FePS for sodium ion batteries of examples 1 to 33XRD (X-ray diffraction) spectrum of the/NC composite negative electrode material;
FIG. 3 shows FePS for sodium ion batteries of examples 1 to 33A charge-discharge cycle chart of a sodium ion battery prepared from the/NC composite negative electrode material under the condition that the current density is 0.1A/g;
FIG. 4 shows FePS for sodium ion batteries of examples 1 to 33A charge-discharge cycle chart of a sodium ion battery prepared from the/NC composite negative electrode material under different current densities;
FIG. 5 shows FePS for sodium ion battery in example 13And the impedance comparison graph of the electrodes before and after the/NC composite negative electrode material is used as the cyclic voltammetry test of the negative electrode of the sodium-ion battery.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects solved by the present invention easier to understand, the present invention will be described in detail with reference to specific embodiments.
Example 1
FePS for sodium ion battery of this example3The preparation method of the/NC composite negative electrode material comprises the following steps:
1) mixing iron powder, red phosphorus powder and sublimed sulfur according to the molar ratio of 1:1:3, fully grinding, transferring to a vacuum tube furnace, and sintering at 750 ℃ for 6d under a vacuum condition to obtain block FePS3A crystal;
2) the obtained block FePS is treated3Putting the crystal into a quartz tube, heating to 500 ℃ at the heating rate of 5 ℃/min under the argon atmosphere, calcining for 2h for annealing treatment, and then sintering the FePS3Dispersing 100mg of crystal in 100mL of deionized water, carrying out ultrasonic treatment for 8h under ice bath condition for stripping, and carrying out freeze drying at-30 ℃ after stripping is finished to obtain FePS3A nano-sheet structured material;
3) the prepared FePS3Adding the nano-sheet structure material and dopamine hydrochloride into a Tris buffer solution according to a mass ratio of 4:1, stirring for 24h for reaction, then carrying out centrifugal separation, washing the solid with deionized water for 3 times, then washing with absolute ethyl alcohol for 3 times, and then carrying out vacuum drying at 60 ℃ for 24h to obtain FePS3@PDA(4:1);
4) The prepared FePS3@ PDA (4:1) is put into an atmosphere furnace and is kept warm for 1h at 500 ℃ in nitrogen atmosphere to prepare carbon-coated nano flaky FePS3FePS of structure3the/NC (4:1) composite material.
FePS for sodium ion battery of this example3the/NC composite negative electrode material is the FePS3the/NC (4:1) composite material.
The sodium ion battery of the embodiment comprises a positive plate, a negative plate, a diaphragm and electrolyte, wherein the positive plate is a metal sodium plate, the negative plate comprises a negative current collector copper foil and a negative material layer coated on the surface of the negative current collector, and the negative material layer comprises a negative electrodeActive material, conductive agent, binder, and negative electrode active material of FePS3The conductive agent is single-walled carbon nanotube, the binder is sodium carboxymethylcellulose, FePS (FePS)3The mass ratio of the/NC (4:1) composite material to the single-walled carbon nanotube to the sodium carboxymethyl cellulose is 7:2: 1. The membrane is glass fiber membrane (Whatman GF/C), and the electrolyte is dissolved with sodium hexafluorophosphate (NaPF)6) Ethylene carbonate and diethyl carbonate (EC: DEC is 1:1, the volume ratio of the mixed solution is 1:1), the mixed solution is used as an electrolyte, and the concentration of sodium hexafluorophosphate in the electrolyte is 1.0 mol/L.
The preparation method of the sodium-ion battery of the embodiment comprises the following steps: the FePS is prepared3Mixing the/NC (4:1) composite material, the single-walled carbon nanotube and the sodium carboxymethyl cellulose according to the mass ratio of 7:2:1, adding an organic solvent, uniformly mixing to prepare slurry, coating the slurry on the surface of copper foil, drying the copper foil in vacuum at 80 ℃ overnight, and cutting to prepare the negative plate. Metal sodium sheet as counter electrode, glass fiber membrane (Whatman GF/C) as diaphragm, and dissolved sodium hexafluorophosphate (NaPF)6) Ethylene carbonate and diethyl carbonate (EC: DEC is 1:1, the volume ratio of the mixed solution is 1:1), the mixed solution is used as an electrolyte, and the concentration of sodium hexafluorophosphate in the electrolyte is 1.0 mol/L. The 2032 coin half cell was assembled in a glove box with argon protection and then left to stand for 16 h.
Example 2
FePS for sodium ion battery of this example3The preparation method of the/NC composite negative electrode material comprises the following steps:
1) mixing iron powder, red phosphorus powder and sublimed sulfur according to the molar ratio of 1:1:3, fully grinding, transferring to a vacuum tube furnace, and sintering at 750 ℃ for 6d under a vacuum condition to obtain block FePS3A crystal;
2) the obtained block FePS is treated3Putting the crystal into a quartz tube, heating to 500 ℃ at the heating rate of 5 ℃/min under the argon atmosphere, calcining for 2h for annealing treatment, and then sintering the FePS3Dispersing 100mg of crystal in 100mL of deionized water, carrying out ultrasonic treatment for 8h under ice bath condition for stripping, and carrying out freeze drying at-30 ℃ after stripping is finished to obtain FePS3A nano-sheet structured material;
3) the prepared FePS3Adding the nano-sheet structure material and dopamine hydrochloride into a Tris buffer solution according to the mass ratio of 3:1, stirring for 24h for reaction, then carrying out centrifugal separation, washing the solid with deionized water for 3 times, then washing with absolute ethyl alcohol for 3 times, and then carrying out vacuum drying at 60 ℃ for 24h to obtain FePS3@PDA(3:1);
4) The prepared FePS3@ PDA (3:1) is put into an atmosphere furnace and is kept warm for 1h at 500 ℃ in nitrogen atmosphere to prepare carbon-coated nano flaky FePS3FePS of structure3the/NC (3:1) composite material.
FePS for sodium ion battery of this example3the/NC composite negative electrode material is the FePS3the/NC (4:1) composite material.
The sodium ion battery of the embodiment comprises a positive plate, a negative plate, a diaphragm and electrolyte, wherein the positive plate is a metal sodium plate, the negative plate comprises a negative current collector copper foil and a negative material layer coated on the surface of the negative current collector, the negative material layer comprises a negative active material, a conductive agent and a binder, and the negative active material is the FePS3The conductive agent is single-walled carbon nanotube, the binder is sodium carboxymethylcellulose, FePS (FePS)3The mass ratio of the/NC (4:1) composite material to the single-walled carbon nanotube to the sodium carboxymethyl cellulose is 7:2: 1. The membrane is glass fiber membrane (Whatman GF/C), and the electrolyte is dissolved with sodium hexafluorophosphate (NaPF)6) Ethylene carbonate and diethyl carbonate (EC: DEC is 1:1, the volume ratio of the mixed solution is 1:1), the mixed solution is used as an electrolyte, and the concentration of sodium hexafluorophosphate in the electrolyte is 1.0 mol/L.
The preparation method of the sodium-ion battery of the embodiment comprises the following steps: the FePS is prepared3Mixing the/NC (4:1) composite material, the single-walled carbon nanotube and the sodium carboxymethyl cellulose according to the mass ratio of 7:2:1, adding an organic solvent, uniformly mixing to prepare slurry, coating the slurry on the surface of copper foil, drying the copper foil in vacuum at 80 ℃ overnight, and cutting to prepare the negative plate. Metal sodium sheet as counter electrode, glass fiber membrane (Whatman GF/C) as diaphragm, and dissolved sodium hexafluorophosphate (NaPF)6) Ethylene carbonate and diethyl carbonate (EC: DEC (decamethylene tetra fluoro ethylene)1:1, volume ratio of the mixed solution 1:1) was used as an electrolyte, and the concentration of sodium hexafluorophosphate in the electrolyte was 1.0 mol/L. The 2032 coin half cell was assembled in a glove box with argon protection and then left to stand for 16 h.
Example 3
FePS for sodium ion battery of this example3The preparation method of the/NC composite negative electrode material comprises the following steps:
1) mixing iron powder, red phosphorus powder and sublimed sulfur according to the molar ratio of 1:1:3, fully grinding, transferring to a vacuum tube furnace, and sintering at 750 ℃ for 6d under a vacuum condition to obtain block FePS3A crystal;
2) the obtained block FePS is treated3Putting the crystal into a quartz tube, heating to 500 ℃ at the heating rate of 5 ℃/min under the argon atmosphere, calcining for 2h for annealing treatment, and then sintering the FePS3Dispersing 100mg of crystal in 100mL of deionized water, carrying out ultrasonic treatment for 8h under ice bath condition for stripping, and carrying out freeze drying at-30 ℃ after stripping is finished to obtain FePS3A nano-sheet structured material;
3) the prepared FePS3Adding the nano-sheet structure material and dopamine hydrochloride into a Tris buffer solution according to the mass ratio of 2:1, stirring for 20h for reaction, then carrying out centrifugal separation, washing the solid with deionized water for 3 times, then washing with absolute ethyl alcohol for 3 times, and then carrying out vacuum drying at 60 ℃ for 24h to obtain FePS3@PDA(2:1);
4) The prepared FePS3@ PDA (2:1) is placed in an atmosphere furnace, and heat preservation is carried out for 1h at 500 ℃ in nitrogen atmosphere, thus obtaining the carbon-coated nano flaky FePS3FePS of structure3the/NC (2:1) composite material.
FePS for sodium ion battery of this example3the/NC composite negative electrode material is the FePS3the/NC (4:1) composite material.
The sodium ion battery comprises a positive plate, a negative plate, a diaphragm and electrolyte, wherein the positive plate is a metal sodium plate, the negative plate comprises a negative current collector copper foil and a negative material layer coated on the surface of the negative current collector, and the negative material layer comprises a negative active material and a conductive agentThe binder and the negative electrode active material are FePS3the/NC (4:1) composite, the rest being the same as in example 2.
The method for preparing the sodium ion battery of this example is the same as that of example 2.
Example 4
FePS for sodium ion battery of this example3The preparation method of the/NC composite negative electrode material comprises the following steps:
1) mixing iron powder, red phosphorus powder and sublimed sulfur according to a molar ratio of 1:1:5, fully grinding, transferring to a vacuum tube furnace, and sintering at 800 ℃ for 3d under a vacuum condition to obtain block FePS3A crystal;
2) the obtained block FePS is treated3Putting the crystal into an atmosphere furnace, heating to 550 ℃ at a heating rate of 10 ℃/min in an argon atmosphere, calcining for 5h for annealing, and then sintering the FePS3Dispersing 100mg of crystal in 80mL of deionized water, carrying out ultrasonic treatment for 7h under ice bath condition for stripping, and carrying out freeze drying at-50 ℃ after stripping is finished to obtain FePS3A nano-sheet structured material;
3) the prepared FePS3Adding the nano-sheet structure material and dopamine hydrochloride into a Tris buffer solution according to a mass ratio of 4:1, stirring for 24h for reaction, then carrying out centrifugal separation, washing the solid with deionized water for 3 times, then washing with absolute ethyl alcohol for 3 times, and then carrying out vacuum drying at 50 ℃ for 48h to obtain FePS3@PDA;
4) The prepared FePS3@ PDA is placed in an atmosphere furnace, and is kept at 600 ℃ for 5 hours in argon atmosphere to prepare carbon-coated nano flaky FePS3FePS of structure3a/NC composite material.
FePS for sodium ion battery of this example3the/NC composite negative electrode material is the FePS3a/NC composite material.
The sodium ion battery comprises a positive plate, a negative plate, a diaphragm and electrolyte, wherein the positive plate is a metal sodium plate, the negative plate comprises a negative current collector copper foil and a negative material layer coated on the surface of the negative current collector, and the negative material layer comprises a negative active material,A conductive agent, a binder, and a negative electrode active material of the FePS3the/NC composite material was otherwise the same as in example 2.
The method for preparing the sodium ion battery of this example is the same as that of example 2.
Example 5
FePS for sodium ion battery of this example3The preparation method of the/NC composite negative electrode material comprises the following steps:
1) mixing iron powder, red phosphorus powder and sublimed sulfur according to a molar ratio of 1:1:4, fully grinding, transferring to a vacuum tube furnace, and sintering at 700 ℃ for 5d under a vacuum condition to obtain block FePS3A crystal;
2) the obtained block FePS is treated3Putting the crystal into an atmosphere furnace, heating to 700 ℃ at a heating rate of 7 ℃/min in an argon atmosphere, calcining for 2h for annealing, and then sintering the FePS3Dispersing 100mg of crystal in 200mL of deionized water, carrying out ultrasonic treatment for 5h under ice bath condition for stripping, and carrying out freeze drying at-50 ℃ after stripping is finished to obtain FePS3A nano-sheet structured material;
3) the prepared FePS3Adding the nano-sheet structure material and dopamine hydrochloride into a Tris buffer solution according to the mass ratio of 3:1, stirring for 45h for reaction, then carrying out centrifugal separation, washing the solid with deionized water for 3 times, then washing with absolute ethyl alcohol for 3 times, and then carrying out vacuum drying at 80 ℃ for 12h to obtain FePS3@PDA;
4) The prepared FePS3@ PDA (2:1) is placed in an atmosphere furnace, and heat preservation is carried out for 2h at 700 ℃ in nitrogen atmosphere, thus obtaining the carbon-coated nano flaky FePS3FePS of structure3a/NC composite material.
FePS for sodium ion battery of this example3the/NC composite negative electrode material is the FePS3a/NC composite material.
The sodium ion battery of the embodiment comprises a positive plate, a negative plate, a diaphragm and electrolyte, wherein the positive plate is a metal sodium plate, the negative plate comprises a negative current collector copper foil and a negative material layer coated on the surface of the negative current collector, and the negative material layer comprises negative active materialA material, a conductive agent, a binder, and a negative electrode active material of the FePS3the/NC composite material was otherwise the same as in example 2.
The method for preparing the sodium ion battery of this example is the same as that of example 2.
Example 6
FePS for sodium ion battery of this example3The preparation method of the/NC composite negative electrode material comprises the following steps:
1) mixing iron powder, red phosphorus powder and sublimed sulfur according to a molar ratio of 1:1:5, fully grinding, transferring to a vacuum tube furnace, and sintering at 600 ℃ for 6d under a vacuum condition to obtain block FePS3A crystal;
2) the obtained block FePS is treated3Putting the crystal into an atmosphere furnace, heating to 300 ℃ at the heating rate of 2 ℃/min in the argon atmosphere, calcining for 10h for annealing treatment, and then sintering the FePS3Dispersing 100mg of crystal in 50mL of deionized water, carrying out ultrasonic treatment for 10h under ice bath condition for stripping, and carrying out freeze drying at-10 ℃ after stripping is finished to obtain FePS3A nano-sheet structured material;
3) the prepared FePS3Adding the nano-sheet structure material and dopamine hydrochloride into a Tris buffer solution according to the mass ratio of 5:1, stirring for 12h for reaction, then carrying out centrifugal separation, washing the solid with deionized water for 3 times, then washing with absolute ethyl alcohol for 3 times, and then carrying out vacuum drying at 60 ℃ for 24h to obtain FePS3@PDA;
4) The prepared FePS3@ PDA is placed in an atmosphere furnace, and heat preservation is carried out for 1h at 800 ℃ in the mixed atmosphere of hydrogen and argon in the volume ratio of 1:3, so as to prepare carbon-coated nano flaky FePS3FePS of structure3a/NC composite material.
FePS for sodium ion battery of this example3the/NC composite negative electrode material is the FePS3a/NC composite material.
The sodium ion battery comprises a positive plate, a negative plate, a diaphragm and electrolyte, wherein the positive plate is a metal sodium plate, and the negative plate comprises a negative current collector copper foil and a negative material coated on the surface of the negative current collectorThe negative electrode material layer comprises a negative electrode active material, a conductive agent and a binder, wherein the negative electrode active material is FePS3the/NC composite material was otherwise the same as in example 2.
The method for preparing the sodium ion battery of this example is the same as that of example 2.
Examples
(1) Topography testing
FePS for sodium ion Battery in example 1 was used3the/NC composite negative electrode material is subjected to SEM test, and the test result is shown in figure 1.
As can be seen from FIG. 1, FePS3the/NC composite negative electrode material is of a lamellar structure, and carbon particles are uniformly attached to the surface of the lamellar structure.
FePS for sodium ion batteries in examples 1 to 3 was used3XRD (X-ray diffraction) test is carried out on the/NC composite negative electrode material, and the test result is shown in figure 2.
As can be seen from fig. 2, in examples 1 to 3, the FePS for sodium ion batteries in example 13FePS on XRD (X-ray diffraction) spectrum of/NC (numerical control) composite negative electrode material3The diffraction peak of (A) is sharpest and obvious, and FePS is on the XRD pattern of the composite cathode material of example 23Second order of diffraction peak of (1), FePS on the spectrum of the composite anode material in example 33The most inconspicuous diffraction peak.
(2) Electrochemical performance test
a. FePS for sodium ion batteries in examples 1 to 3 was used3The sodium ion battery prepared from the/NC composite negative electrode material is subjected to charge-discharge cycle test at a constant temperature of 28 ℃ and a current density of 0.1A/g, and the test result is shown in figure 3.
As can be seen from fig. 3, the FePS for sodium ion batteries in examples 1 to 33The sodium ion battery prepared from the/NC composite negative electrode material has good discharge cycle stability at 0.1A/g, almost no discharge capacity attenuation after 90 times of cycle, and slightly increased discharge capacity. As is obvious from FIG. 3, the sodium ion battery of example 1 has the largest specific discharge capacity, can still maintain the specific discharge capacity of more than 555mAh/g after being cycled for 90 times, and the most of the cycled specific discharge capacity is more than 520mAh/g, and is implementedThe discharge capacity of the sodium-ion battery in example 2 is about 450mAh/g, the first discharge specific capacity of the sodium-ion battery in example 3 is 614mAh/g under the current density of 0.1A/g, and the discharge specific capacity after 90 times of circulation is about 403 mAh/g.
b. FePS for sodium ion Battery in example 1 was used3The sodium ion battery prepared from the/NC composite negative electrode material is subjected to charge-discharge cycles at constant temperature of 28 ℃ and current densities of 0.1A/g, 0.2A/g, 0.5A/g, 1A/g, 2A/g and 5A/g, and the test result is shown in figure 4.
As can be seen from FIG. 4, the sodium ion battery of example 1 is excellent in rate discharge performance, and the discharge capacity is about 500mAh/g at 0.1A/g, about 400mAh/g at 1A/g, and about 300mAh/g at 5A/g.
c. FePS for sodium ion Battery in example 1 was used3The negative electrode of the sodium ion battery prepared from the/NC composite negative electrode material is subjected to an electrochemical impedance test, and the test result is shown in figure 5.
As can be seen from fig. 5, the impedance of the electrode before the cyclic voltammetry test is large, and the impedance of the electrode after the cyclic voltammetry test is significantly smaller than that before the test.
Claims (8)
1. FePS for sodium ion battery3The preparation method of the/NC composite negative electrode material is characterized by comprising the following steps: the method comprises the following steps:
1) FePS is prepared3Adding dopamine hydrochloride into alkaline solution, stirring for 12-48h, and carrying out solid-liquid separation to obtain FePS3@ PDA material; the alkaline solution is a Tris buffer solution;
2) FePS prepared in the step 1)3The @ PDA material is subjected to heat preservation for 1-5h at 800 ℃ in a reducing atmosphere or an inert atmosphere to obtain the material;
the FePS3The mass ratio of the dopamine hydrochloride to the dopamine hydrochloride is 4: 1;
the FePS3Is prepared by the method comprising the following steps:
a) uniformly grinding iron powder, phosphorus powder and sulfur powder, and then sintering in vacuum at 600-800 ℃ for 3-6d to obtain block FePS3A crystal;
b) the block FePS prepared in the step a) is3Calcining the crystal for 2-10h at the temperature of 300-700 ℃ under the inert atmosphere;
c) uniformly mixing the calcined material obtained in the step b) with water to obtain a mixed solution, carrying out ultrasonic treatment on the mixed solution for 5-10 hours, and carrying out freeze drying.
2. FePS for sodium ion battery according to claim 13The preparation method of the/NC composite negative electrode material is characterized by comprising the following steps: washing and vacuum drying the solid obtained after solid-liquid separation in the step 1); the washing is that the washing is firstly carried out for more than 3 times by using deionized water, and then the washing is carried out for more than three times by using absolute ethyl alcohol.
3. FePS for sodium ion battery according to claim 23The preparation method of the/NC composite negative electrode material is characterized by comprising the following steps: the temperature of the vacuum drying is 50-80 ℃, and the time of the vacuum drying is 12-48 h.
4. FePS for sodium ion battery according to claim 13The preparation method of the/NC composite negative electrode material is characterized by comprising the following steps: the molar ratio of the iron powder to the phosphorus powder to the sulfur powder in the step a) is 1:1: 3-5.
5. FePS for sodium ion battery according to claim 13The preparation method of the/NC composite negative electrode material is characterized by comprising the following steps: in step b) the bulk FePS is reacted under an inert gas atmosphere3The temperature of the crystal is raised to 300-700 ℃ at the speed of 1-10 ℃/min.
6. FePS for sodium ion battery according to claim 13The preparation method of the/NC composite negative electrode material is characterized by comprising the following steps: the sonication in step c) is carried out under ice bath conditions.
7. FePS for sodium ion battery prepared by the preparation method of claim 13the/NC composite negative electrode material.
8. The utility model provides a sodium ion battery, includes positive pole, negative pole, diaphragm, electrolyte, the negative pole includes negative current collector copper foil and the negative material layer of coating on negative current collector surface, the negative material layer includes negative active material, conducting agent, binder, its characterized in that: the negative electrode active material is FePS according to claim 73the/NC composite negative electrode material.
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CN108183269A (en) * | 2018-01-09 | 2018-06-19 | 东莞市联洲知识产权运营管理有限公司 | A kind of preparation method of water system high magnification sodium-ion battery |
CN108807945A (en) * | 2018-07-27 | 2018-11-13 | 上海工程技术大学 | Redox graphene/stannate anode material of lithium-ion battery and its preparation method and application |
CN109167035A (en) * | 2018-08-22 | 2019-01-08 | 郑州大学 | Carbon-coated ferrous sulfide negative electrode material, preparation method and its sodium-ion battery of preparation |
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CN108183269A (en) * | 2018-01-09 | 2018-06-19 | 东莞市联洲知识产权运营管理有限公司 | A kind of preparation method of water system high magnification sodium-ion battery |
CN108807945A (en) * | 2018-07-27 | 2018-11-13 | 上海工程技术大学 | Redox graphene/stannate anode material of lithium-ion battery and its preparation method and application |
CN109167035A (en) * | 2018-08-22 | 2019-01-08 | 郑州大学 | Carbon-coated ferrous sulfide negative electrode material, preparation method and its sodium-ion battery of preparation |
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