CN114899365B - Phosphate ion doped SnS crystal/nitrogen doped rGO composite material and preparation method and application thereof - Google Patents
Phosphate ion doped SnS crystal/nitrogen doped rGO composite material and preparation method and application thereof Download PDFInfo
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 239000013078 crystal Substances 0.000 title claims abstract description 38
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 38
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 31
- 229940085991 phosphate ion Drugs 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims abstract description 31
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims abstract description 31
- 235000002949 phytic acid Nutrition 0.000 claims abstract description 31
- 229940068041 phytic acid Drugs 0.000 claims abstract description 31
- 239000000467 phytic acid Substances 0.000 claims abstract description 31
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 24
- 239000002135 nanosheet Substances 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 229910052718 tin Inorganic materials 0.000 claims abstract description 5
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 3
- 239000010452 phosphate Substances 0.000 claims abstract description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 20
- 229920000877 Melamine resin Polymers 0.000 claims description 18
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 229910052717 sulfur Inorganic materials 0.000 claims description 13
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- 229910021389 graphene Inorganic materials 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000007773 negative electrode material Substances 0.000 claims description 9
- 239000011593 sulfur Substances 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea group Chemical group NC(=S)N UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 4
- 238000004108 freeze drying Methods 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 125000004434 sulfur atom Chemical group 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000012300 argon atmosphere Substances 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 125000004437 phosphorous atom Chemical group 0.000 claims description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 2
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 2
- 238000009830 intercalation Methods 0.000 abstract description 5
- 230000002687 intercalation Effects 0.000 abstract description 5
- 238000009831 deintercalation Methods 0.000 abstract description 3
- 230000006872 improvement Effects 0.000 abstract description 2
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- 229910052698 phosphorus Inorganic materials 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000011574 phosphorus Substances 0.000 description 8
- 239000002028 Biomass Substances 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 6
- 230000001351 cycling effect Effects 0.000 description 6
- 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 5
- 150000002500 ions Chemical class 0.000 description 5
- 230000002441 reversible effect Effects 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 239000010405 anode material Substances 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052976 metal sulfide Inorganic materials 0.000 description 4
- 239000002064 nanoplatelet Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 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 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- AAMATCKFMHVIDO-UHFFFAOYSA-N azane;1h-pyrrole Chemical compound N.C=1C=CNC=1 AAMATCKFMHVIDO-UHFFFAOYSA-N 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000003010 ionic group Chemical group 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 150000003623 transition metal compounds Chemical class 0.000 description 2
- QDZOEBFLNHCSSF-PFFBOGFISA-N (2S)-2-[[(2R)-2-[[(2S)-1-[(2S)-6-amino-2-[[(2S)-1-[(2R)-2-amino-5-carbamimidamidopentanoyl]pyrrolidine-2-carbonyl]amino]hexanoyl]pyrrolidine-2-carbonyl]amino]-3-(1H-indol-3-yl)propanoyl]amino]-N-[(2R)-1-[[(2S)-1-[[(2R)-1-[[(2S)-1-[[(2S)-1-amino-4-methyl-1-oxopentan-2-yl]amino]-4-methyl-1-oxopentan-2-yl]amino]-3-(1H-indol-3-yl)-1-oxopropan-2-yl]amino]-1-oxo-3-phenylpropan-2-yl]amino]-3-(1H-indol-3-yl)-1-oxopropan-2-yl]pentanediamide Chemical compound C([C@@H](C(=O)N[C@H](CC=1C2=CC=CC=C2NC=1)C(=O)N[C@@H](CC(C)C)C(=O)N[C@@H](CC(C)C)C(N)=O)NC(=O)[C@@H](CC=1C2=CC=CC=C2NC=1)NC(=O)[C@H](CCC(N)=O)NC(=O)[C@@H](CC=1C2=CC=CC=C2NC=1)NC(=O)[C@H]1N(CCC1)C(=O)[C@H](CCCCN)NC(=O)[C@H]1N(CCC1)C(=O)[C@H](N)CCCNC(N)=N)C1=CC=CC=C1 QDZOEBFLNHCSSF-PFFBOGFISA-N 0.000 description 1
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 102100024304 Protachykinin-1 Human genes 0.000 description 1
- 101800003906 Substance P Proteins 0.000 description 1
- 241001506047 Tremella Species 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000003658 microfiber Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- H01M4/58—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
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- 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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Composite Materials (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a phosphate ion doped SnS crystal/nitrogen doped rGO composite material, and a preparation method and application thereof, and belongs to the field of battery materials. The composite material consists of a nitrogen-doped rGO nano sheet and a phosphate ion-doped SnS nano sheet deposited on the surface of the nitrogen-doped rGO nano sheet, wherein the doped SnS crystal has a SnS crystal structure and PO 4 3‑ And embedded between SnS lattice layers, and Sn and O, O are bonded with P through covalent bonds. The invention uses the phytic acid to be injected into the SnS crystal lattice, realizes the remarkable improvement of the intrinsic electron conductivity of the SnS, and simultaneously effectively relieves the volume expansion problem caused by the intercalation/deintercalation of sodium ions of the SnS crystal.
Description
Technical Field
The invention relates to a phosphate ion doped SnS crystal/nitrogen doped rGO composite material, and a preparation method and application thereof, and belongs to the field of battery materials.
Background
As a powerful support for renewable and sustainable energy sources, the development of efficient energy storage technologies is of great importance. In order to alleviate the pressure caused by the lack of energy and the deterioration of environment, the utilization of clean renewable energy has become a necessary requirement for the global energy revolution and green development. The utilization of non-petrochemical clean new energy is greatly promoted, the efficiency of the energy storage system is improved, and the clean low-carbon development is realized. The secondary battery is used as a main energy storage technology capable of converting other forms of energy into electric energy and storing the electric energy in a chemical energy form, and is subjected to new development opportunities in new energy transformation and energy structure upgrading. Sodium Ion Batteries (SIBs) have attracted much attention as a new generation of alkali metal ion batteries due to their abundant natural reserves and lower cost effectiveness. Numerous studies have shown that the key to the electrochemical performance of batteries is the energy storage density and power density, which are largely dependent on the performance of the positive and negative electrode materials.
Among the different negative electrode material choices, metal sulfides with high theoretical capacities and energy densities are considered as promising candidates for developing high capacity and long life SIBs. As the representation of metal sulfide, snS with unique lamellar structure combines with special physical and chemical characteristics, including obvious semiconductor characteristics, ferroelectric/piezoelectricity in structural plane, etc., and provides an ideal platform for high-performance cathode research. Currently, the main problems with the use of SnS in SIBs are still their severe volume expansion and extremely poor electron conductivity. In the sodium ion intercalation/deintercalation process, the lamellar structure of SnS is severely stacked, causes irreversible phase change and causes pulverization of active materials, thereby causing continuous occurrence of side reactions and deterioration of cycle performance.
Existing methods can increase electron/ion conductivity through external modification, but they cannot effectively increase the intrinsic conductivity of SnS. To solve this problem, nonmetallic heteroatom doping (N, C, O and P) has been demonstrated to improve goldBelongs to a very effective method for sulfide intrinsic conductivity and electron/ion mobility. In addition to nonmetallic heteroatom doping, the doping or intercalation of macromolecular or nonmetallic ionic groups is also an effective way to induce lattice distortion. Doping or intercalation of ionic groups has been shown to modulate the band structure to increase conductivity and provide more active sites for metal sulfides, thereby improving electrochemical performance. More recently, phosphate ions (PO 4 3- ) Due to the doping thereofIs of great concern due to its large ionic radius and high electronegativity. On the one hand, phosphate ions with large ionic radius can be used as doping sites to be introduced between layers, so as to increase the interlayer spacing of sulfide, thereby promoting Na + Is transferred from the first to the second transfer station. On the other hand, phosphate ions having high electronegativity may replace S atoms of sulfides to form O-metal bonds, thereby improving the intrinsic conductivity of the metal sulfides and promoting electron transfer. Thus, by PO 4 3- Doping further improves the electrochemical performance of SnS is reasonable.
Disclosure of Invention
In view of the above problems, the invention aims to provide a method for improving the intrinsic conductivity of SnS, which is applied to a negative electrode material of a sodium ion battery. Meanwhile, compared with unsafe phosphorus sources, the ecological environment-friendly nontoxic biomass phosphorus source is more attractive, and the efficient and stable sodium ion battery anode material is prepared through a safer and quicker synthesis process.
In order to solve the problems in the prior art, the invention provides a method for realizing efficient and stable sodium storage by implanting phosphate ions into SnS crystals, which prepares PO through one-step hydrothermal process 4 3- Doped SnS while achieving high pyridine nitrogen doping in the carbon matrix material. PO (Positive oxide) 4 3- The directional doping is constructed in the SnS crystal in a Sn-O-P covalent bond form, so that the directional doping has definite doping sites, the lattice spacing of the SnS is effectively increased, and meanwhile, the electron conductivity of the SnS is remarkably improved. With the help of controllable and advantageous heteroatom doping, the intrinsic reaction kinetics of SnS can be greatly enhanced, and the capacity is causedThe increase in quantity and energy/power density and good cycling stability. Introduction of PO by Biomass phosphorus source 4 3- The groups are used for realizing the modification of a layered structure and the efficient and stable sodium ion battery cathode material. This concept is not limited to SnS alone, but is likely to extend to a wider range of layered structures and transition metal compounds. And the phytic acid is used as a phosphorus source, so that the biomass material is effectively utilized, and the research concept is green and environment-friendly. The whole preparation process has the advantages of simple steps, mild conditions, good stability, low energy consumption, small influence on environment and remarkable advantages.
In order to achieve the above purpose, the main technical scheme adopted by the invention comprises the following steps:
a phosphate ion doped SnS crystal/nitrogen doped rGO composite material consists of a nitrogen doped rGO (reduced graphene oxide) nanosheet and a phosphate ion doped SnS nanosheet deposited on the surface of the composite material, wherein the doped SnS crystal has a SnS crystal structure and PO 4 3- And embedded between SnS lattice layers, and Sn and O, O are bonded with P through covalent bonds.
The phosphate ion doped SnS crystal/nitrogen doped rGO composite material is herein denoted as PO 4 -SnS/NG composite.
In the SnS nano-sheet doped with phosphate ions, the invention shows that P is PO 4 3- In the form of a composite system comprising Sn-O-P covalent bonds, i.e. PO 4 3- Is covalently bound to SnS and exists in the lattice space.
The size of the phosphate ion doped SnS crystal/nitrogen doped rGO composite material is 10-35 nm. Further, the SnS nanoplatelets have a thickness of 9nm.
In the phosphate ion doped SnS crystal, the PO 4 3- The doping amount is 1.0 to 4.0%, preferably 3.32%, in terms of atomic percent of phosphorus atoms in the composite material.
In the nitrogen-doped rGO nano-sheet, the existence forms of the doped nitrogen are pyridine nitrogen, pyrrole nitrogen and graphite nitrogen, and the nitrogen is mainly pyridine nitrogen, and the pyridine nitrogen is helpful for improving the adsorption effect of the electrode material on sodium ions.
Preferably, the nitrogen-doped rGO nanoplatelets have pyridine nitrogen, pyrrole nitrogen and graphite nitrogen contents of 67.82%, 26.58% and 5.6%.
The invention also aims to provide a preparation method of the phosphate ion doped SnS crystal/nitrogen doped rGO composite material.
A preparation method of a phosphate ion doped SnS crystal/nitrogen doped rGO composite material comprises the steps of taking tin salt, a sulfur source, a graphene oxide aqueous solution, melamine and phytic acid as raw materials for carrying out a hydrothermal reaction, collecting precipitate after the reaction is finished, and freeze-drying to obtain a composite material precursor; and (3) placing the composite material precursor in an inert atmosphere for roasting to obtain the phosphate ion doped SnS crystal/nitrogen doped rGO composite material.
In the technical scheme, the biomass phytic acid is adopted for selecting the phosphorus source in the reaction system. Phytic acid, also known as phytic acid, is mainly found in the seeds, roots and stems of plants. The phytic acid contains 6 mutually symmetrical phosphate groups, and the symmetrical structure has good conductivity. And the phosphate group has a strong coordination effect with most metal cations, and a phytic acid metal cross-linking structure is easy to form. Melamine is selected as the nitrogen source for nitrogen doping. The hydrogen bonding effect between the phytic acid and the melamine effectively regulates the ratio of different nitrogen types in nitrogen doping. PO with large ion radius 4 3- Introducing SnS interlayer as doping site to increase interlayer spacing of sulfide to promote Na + Is transferred from the first to the second transfer station.
Preferably, the temperature of the hydrothermal reaction is 160-180 ℃ and the reaction time is 10-12 h.
Preferably, the tin salt, the sulfur source and the tin atoms in the melamine: sulfur atom: the molar ratio of melamine is 2:2:5; the ratio of the phytic acid to the melamine is 0.5-2 mL to 5mol; the volume ratio of the phytic acid to the graphene oxide aqueous solution is 0.5-2:65, wherein the concentration of the graphene oxide aqueous solution is 2mg mL -1 。
Preferably, the composite material precursor is placed in nitrogen or argon atmosphere and baked for 2-6 hours at 400-600 ℃ to obtain the SnS crystal doped with phosphate ions.
Preferably, the tin salt is SnCl 4 ·5H 2 O、SnCl 2 . The sulfur source is thiourea, thioacetamide and sodium sulfide.
The invention also aims to provide the application of the phosphate ion doped SnS crystal/nitrogen doped rGO composite material as a negative electrode material of a sodium ion battery.
The beneficial effects of the invention are as follows:
(1) Aiming at the problems of serious volume expansion and extremely poor electron conductivity of SnS, the invention uses the phytic acid to be injected into the SnS crystal lattice, thereby realizing the remarkable improvement of the intrinsic electron conductivity of the SnS and simultaneously effectively relieving the volume expansion problem of the SnS crystal caused by the embedding/extraction of sodium ions.
(2) Preparation of PO by one-step hydrothermal process 4 3- Doped SnS while achieving high pyridine nitrogen doping in the carbon matrix material. The presence of phytic acid in the system modifies the intrinsic crystal structure of SnS and affects the electron/ion states, band gap and crystal structure stability for sodium ion storage. PO (Positive oxide) 4 3- The implantation of (a) results in charge redistribution of the SnS crystal unit cells, in particular charge distortion on surface atoms and promotes electron transport. In addition, the phytic acid has another effect of regulating the nitrogen doping configuration, so that the content of pyridine nitrogen in the carbon matrix is up to 67.82%, and the electronic conductivity and the chemical activity are effectively improved, thereby improving the electronic/Na + And provides greater capacity.
(3) The invention has no expensive raw materials and accords with the low-cost concept of the sodium ion battery. The preparation process uses phytic acid as a phosphorus source, does not use toxic solvents, and is environment-friendly. Realizes the effective utilization of biomass materials, and the research concept is green and environment-friendly.
(4) The sodium ion battery anode material PO prepared by the method of the invention 4 SnS/NG with excellent specific capacity and very long cycle life (at 2A g -1 The specific capacity after 10000 cycles is kept at 186.4mA h g under the current density of (2) -1 The attenuation rate of the capacity per cycle is only 0.0028 percent, and the performance requirement on the negative electrode material of the sodium ion battery is met.
(5) The PO is obtained by roasting the precursor after a one-step hydrothermal method 4 The SnS/NG composite material has the advantages of simple process, mild operation condition, good stability, low energy consumption and small influence on environment, and can be produced commercially.
The invention uses PO 4 3- The directional doping (Sn-O-P covalent bond) is built in the SnS crystal, so that the directional doping has definite doping positions, the lattice spacing of the SnS is effectively increased, and meanwhile, the electron conductivity of the SnS is remarkably improved. With the aid of a controlled, advantageous doping of heteroatoms, the intrinsic reaction kinetics of SnS can be greatly enhanced and lead to an increase in capacity and energy/power density and good cycling stability. Introduction of PO by Biomass phosphorus source 4 3- The groups are used for realizing the modification of a layered structure and the efficient and stable sodium ion battery cathode material. This concept is not limited to SnS but is likely to extend to a wider range of layered structures and transition metal compounds, providing a new research perspective for sodium ion battery anode materials.
Drawings
FIGS. 1 (a) - (h) are products PO of example 1 4 -morphology characterization graphs of the SnS/NG composite material under different magnifications; FIG. 1 (i) is the product PO of example 1 4 SnS/NG composite energy dispersive X-ray spectrogram.
FIG. 2 is the product PO of example 1 4 -SnS/NG composite XRD pattern.
FIGS. 3 (a) - (f) are products PO of example 2 4 -SnS/NG composite XPS map.
FIGS. 4 (a) - (e) are products PO of example 3 4 Sodium storage properties of the SnS/NG composite.
FIGS. 5 (a) - (e) are products PO of example 4 4 Electrochemical performance curves tested after sodium ion full cells were assembled at the negative electrode of sodium ion cells made of SnS/NG composite material.
FIG. 6 is a PO according to the invention 4 -SnS/NG composite microstructure schematic.
Detailed Description
The following non-limiting examples will enable those of ordinary skill in the art to more fully understand the invention and are not intended to limit the invention in any way.
The test methods described in the following examples, unless otherwise specified, are all conventional; the reagents and materials, unless otherwise specified, are commercially available.
The basic idea of the invention is that 0.5-2 mL of phytic acid, 2mmol of tin salt (calculated by tin atom), 2mmol of sulfur source (calculated by sulfur atom), 5mmol of melamine and 65mL (2 mg mL) -1 ) The Graphene Oxide (GO) aqueous solution is used as a raw material, and the SnS and high pyridine nitrogen doped rGO composite material containing phosphate is prepared by a simple preparation process, and the product is used for preparing a negative electrode material of a sodium ion battery, so that the sodium ion battery can obtain excellent charge-discharge specific capacity and ideal cycle stability.
The invention provides a preparation method of a phosphate ion doped SnS crystal/nitrogen doped rGO composite material, which comprises the following steps:
s1: one-step hydrothermal method for preparing phosphate ions (PO) deposited and grown on nitrogen-doped reduced graphene oxide matrix 4 3- ) The SnS crystals were implanted (note: PO (Positive oxide) 4 SnS/NG) taking tin salt, sulfur source, graphite oxide, melamine and phytic acid as raw materials, performing hydrothermal reaction, collecting precipitate after the reaction is finished, freeze-drying to obtain a composite material precursor, and roasting the composite material precursor in inert atmosphere to obtain PO 4 -SnS/NG composite.
Specifically, biomass phytic acid is adopted for the selection of the phosphorus source in the reaction system. The ratio of the phytic acid to other raw materials in the system comprises 0.5-2 mL of phytic acid, 2mmol of tin salt, 2mmol of sulfur source, 5mmol of melamine and 65mL (2 mg mL) -1 ) GO aqueous solution.
Melamine is selected as the nitrogen source for nitrogen doping. The hydrogen bonding effect between the phytic acid and the melamine effectively regulates the ratio of different nitrogen types in nitrogen doping. PO with high electronegativity 4 3- Is embedded into SnS crystal lattice through Sn-O-P covalent bond form, thereby improving metal sulfurIntrinsic conductivity of the compound and promotes electron transfer.
The temperature of the hydrothermal reaction is 160-180 ℃ and the reaction time is 10-12 h. Placing the composite material precursor in nitrogen or argon atmosphere, roasting for 2-6 h at 400-600 ℃ to obtain PO 4 -SnS/NG composite.
In order to further explain the technical effects of the present invention, the following description will be given with reference to specific examples.
Example 1
1. PO (Positive oxide) 4 Characterization of morphology of SnS/NG composite materials
Phosphate ions (PO) deposited and grown on nitrogen-doped reduced graphene oxide nanosheet substrate are prepared by one-step hydrothermal method 4 3- ) Implanting SnS crystals: the system comprises 1mL of phytic acid and 2mmol of SnCl 4 ·5H 2 O, 2mmol thiourea, 5mmol melamine and 65mL (2 mg mL) -1 ) Carrying out hydrothermal reaction (12 h at 180 ℃) on GO aqueous solution, collecting precipitate after the reaction is finished (deionized water/absolute ethyl alcohol are respectively washed three times), freeze-drying to obtain a composite material precursor, and placing the composite material precursor in N 2 Calcining in atmosphere (500 ℃ for 4 h) to obtain PO 4 -SnS/NG composite.
Meanwhile, in order to deeply investigate the effect of phytic acid in the reaction system, a control group, namely identical reaction conditions, was prepared in example 1 except that phytic acid was not added to the reaction system, and the obtained sample was recorded as SnS/NG.
Referring to FIG. 1, the product PO of this example 4 -SnS/NG composite SEM and TEM images. Under different magnification, a 3D tremella layered structure is presented. PO (Positive oxide) 4 The SnS nanoplatelets in SnS/NG are deposited in large amounts on the high pyridine nitrogen doped rGO surface, making its surface more wrinkled and fluffy (fig. 1 a-b). The layered micro-nano structure forms a conductive network which is communicated with each other, and contains rich reactive sites and ion/electron diffusion channels. The absence of particles in the product suggests that SnS is uniformly deposited on the nitrogen doped rGO flakes, which is also supported by TEM images and elemental mapping. At PO 4 As can be seen from the SnS/NG TEM images (FIGS. 1 c-d), there is a well-distributed particle size of 10-35nm SnS nanoplatelets. The HRTEM images (fig. 1 e-h) detected sharp lattice fringes at pitches 0.348, 0.330, 0.286, 0.282, and 0.298, corresponding to lattice distances of the (120) (021) (111) (040) and (101) planes of SnS, respectively. The remarkable reduction of the size of SnS and the increase of the lattice spacing show that the introduction of the phytic acid can be injected into the SnS lattice and effectively inhibit the growth of microcrystals. FIG. 1i shows the result of element mapping, revealing PO 4 Uniform distribution of Sn, S, C, N and P elements in SnS/NG samples, while demonstrating the presence of P species.
Referring to FIG. 2, XRD patterns of samples of the present invention, snS/NG and PO 4 The SnS/NG samples all show similar characteristic diffraction peaks, corresponding to the standard rhombic phase SnS (JCPDS 39-0354). Furthermore, PO 4 The main peak of the SnS/NG composite material is shifted towards the direction of low diffraction angle, indicating PO 4 3- Is introduced to enable PO 4 The interlayer spacing of SnS/NG increases, which is consistent with TEM results.
2. PO (Positive oxide) 4 -SnS/NG composite structural characterization
Referring to FIG. 3, the PO was carefully studied by XPS 4 -chemical states and compositions of SnS/NG and SnS/NG. Compared with SnS/NG, in PO 4 P signal was found in SnS/NG, indicating successful introduction of P species. As shown in fig. 3. In the P2P spectrum, there is a spectrum of the SnP located at 139eV and 133eV 2 O 7 The characteristic peak corresponding to the P-C bond, PO was present at 134eV 4 3- Corresponding characteristic peaks. Indicating substance P as PO 4 3- Form(s) present in PO 4 SnS/NG system. In the O1s spectrum, a characteristic peak corresponding to Sn-O-P appears at 531.5, which is fully confirmed by PO 4 3- Is covalently bound as SnS, and exists in the lattice spacing. PO (Positive oxide) 4 In the high-resolution Sn 3d and S2 p spectra of SnS/NG (FIGS. 3 c-d), it is observed that the binding energy is shifted by 0.2 eV and 0.1eV respectively towards the higher energy direction, which indicates that the surrounding environment of atoms in the system is changed, and the binding energy of electrons in the inner layer is increased due to the fact that the atoms are bonded with atoms with high electronegativity. Thus, PO 4 The higher bond energy in SnS/NG is due to PO 4 3- Because it has a high electronegativity. As shown in FIGS. 3e-f, snS/NG andPO 4 the pyridine-N, pyrrole-N, graphite-N content in SnS/NG were 46.91%/67.82%, 36.23%/26.58% and 16.86%/5.6%, respectively. PO (Positive oxide) 4 The content of pyridine-N in the SnS/NG system is obviously increased and the content of graphite-N is obviously reduced. The hydrogen bond and chelation between phytic acid and melamine effectively regulate and control the nitrogen type. Single or three N pyridine vacancies created by pyridine nitrogen doping can enhance sodium storage and rate performance.
3. PO (Positive oxide) 4 Sodium storage Property of SnS/NG composite Material
PO obtained in this example 4 The SnS/NG composite material is used as an active material of a negative electrode of a sodium ion battery, and is mixed with acetylene black and a binder PVDF/NMP according to a mass ratio of 70:20:10, and then coating the mixture on a copper foil to form a film. Vacuum drying at 80deg.C for 12 hr, cutting and tabletting, wherein the weight of active substance in electrode sheet is 1.2mg cm -2 Left and right. The metallic sodium sheet was used as a counter electrode, and a sodium perchlorate electrolyte (NC-008), whatman glass microfiber membrane, model GF/D, was used to assemble a CR2032 button half cell in an argon-filled glove box. In the experiment, a LAND2001CT battery performance tester is adopted to test the charge-discharge and cycle performance, and the voltage range is 0.01-3.0V. The battery was tested for rate performance and coulombic efficiency curves, the results are shown in fig. 4.
To characterize PO 4 Electrochemical properties of the SnS/NG composite material, in this example, two sets of comparison samples of both SnS/NG and SnS/G composite materials are also present. Namely, the identical reaction conditions are adopted, and only the phytic acid is not added in the reaction system, the obtained sample is recorded as SnS/NG, and the sample without phytic acid and melamine added in the system is recorded as SnS/G.
FIG. 4a is PO 4 SnS/NG at 0.2A g -1 Constant current charge and discharge curves for the 1 st, 2 nd, 20 th, 50 th, 100 th and200 th cycles at current density. The initial charge-discharge specific capacity is 452.3/1056.4mA h g -1 The Initial Coulombic Efficiency (ICE) is about 42.8%, and the irreversible capacity loss may be related to the generation of the SEI layer and the decomposition of the electrolyte. PO (Positive oxide) 4 The overlap of the GDC curves of the SnS/NG electrodes starting from the 2 nd cycle is excellent. The coulomb efficiency of the second cycle increased to 93.16%, with the cycling cycleThe number is increased, the electrode is well activated, and the high coulombic efficiency of the subsequent circulation is improved>99%) also confirms PO 4 Good reversibility of SnS/NG during charge and discharge. FIG. 4b shows three electrode materials at 0.2. 0.2A g -1 Cycling performance curve at current density. After 300 cycles, the SnS/NG and SnS/G electrodes can only provide 144.3mA h G -1 And 111.4mA h g -1 And PO(s) 4 The highest reversible capacity of 445.1mA h g is maintained by the SnS/NG electrode -1 The corresponding capacity retention was 98.4% and capacity fade per cycle was only 0.0053%. FIG. 4c study PO 4 Rate capability of SnS/NG, snS/NG and SnS/G, where PO 4 The SnS/NG electrode shows the best performance. At 0.1, 0.2, 0.5, 1.0, 2.0 and 5.0A g -1 PO at current density of (2) 4 Reversible capacities of the SnS/NG electrodes are 476.1, 427.0, 364.5, 324.7, 276.9, 219.9mA h g, respectively -1 . Even at 10A g -1 In the case of (2), 182.0mA h g can be maintained -1 Is a high capacity of (a). When the current density is switched to 0.1A g -1 At the time of PO 4 The capacity of the SnS/NG electrode can be restored to 452.7mA h g -1 . When the current density decreases, PO 4 The reversible capacity of the SnS/NG material can be basically restored to the initial value, and the excellent rate performance is shown. Further test of PO 4 SnS/NG at 1.0 and 5.0A g -1 Long-term cycling stability at current density to better evaluate electrochemical performance. As shown in FIG. 4d, at 1.0A g -1 After 1500 cycles, PO 4 The SnS/NG electrode provides 380.5mA hg -1 The capacity retention was 95%, and the capacity fade per cycle was 0.0033%. When the current density increases to 5.0. 5.0A g -1 At the time of PO 4 The SnS/NG electrode can still provide 184.2mA hg in 10000 cycles -1 Exhibits excellent high-rate cycle performance, and the capacity fade rate per cycle is only 0.0028%. The results show that PO 4 SnS/NG has good electrochemical properties and excellent sodium ion intercalation/deintercalation kinetics. Notably, few Sn-based materials exhibit such very long cycle life and cycling in sodium ion batteries compared to previously reported resultsStability.
4. PO (Positive oxide) 4 SnS/NG composite assembled full cell
Referring to fig. 5, in order to evaluate the anode material PO 4 Application feasibility of SnS/NG, successful PO Assembly 4 -SnS/CN//Na 3 V 2 (PO 4 ) 3 Sodium ion full cell. The current density and specific capacity of the full cell were measured with the quality of the negative electrode material as a standard. The full cell was tested at a voltage range of 0.01-4V. Based on the quality of the negative electrode, the full cell is 1Ag -1 Can show 221.6mAh g after 300 times of circulation -1 The capacity retention rate was 65.2% and the capacity fade rate per cycle was 0.116% (fig. 5 a). The full cell also exhibited good rate performance at 0.1, 0.2, 0.5, 1.0, 2.0 and 5.0Ag -1 The reversible capacity is 418.2, 355.5, 316.5, 282.9, 254.9, 223.5mA h g under the current density -1 . When the current density returns to 0.1Ag -1 When the reversible capacity is recovered to 356.8mA h g -1 The stability of the negative electrode material was demonstrated (fig. 5 b). The whole cell is 0.1-5Ag -1 The charge-discharge curve at current density, the curve trend shows excellent similarity, and the average output voltage is about 2.5V (fig. 5 c).
According to PO 4 -SnS/NG negative electrode and Na 3 V 2 (PO 4 ) 3 The total mass of the positive electrode calculated the capacity of the full cell to obtain a Ragone plot (fig. 5 d). Full cell at 0.18kW kg -1 Exhibits a power density of 399.3Wh kg -1 Is a high energy density of (a). Even if the power density is increased to 2.75kW kg -1 The energy density is still kept at 247.4Wh kg -1 . The assembled button full cell can power a series of LED lights (fig. 5 e). These encouraging results again verify the PO 4 Advantages of SnS/NG electrodes in practical applications of SIBs cathodes.
Claims (9)
1. The utility model provides a phosphate ion doped SnS crystal/nitrogen doped rGO combined material which characterized in that: the composite material consists of a nitrogen-doped rGO nano-sheet and a phosphate ion-doped SnS nano-sheet deposited on the surface of the nitrogen-doped rGO nano-sheet, whereinThe doped SnS crystal has a SnS crystal structure and PO 4 3- And embedded between SnS lattice layers, and Sn and O, O are bonded with P through covalent bonds.
2. A material according to claim 1, characterized in that: the size of the phosphate ion doped SnS nano-sheet is 10-35 nm.
3. A material according to claim 1, characterized in that: the PO (PO) 4 3- The doping amount is 1.0-4.0% based on the atomic percentage of phosphorus atoms in the composite material.
4. A preparation method of a phosphate ion doped SnS crystal/nitrogen doped rGO composite material is characterized by comprising the following steps: taking tin salt, a sulfur source, a graphene oxide aqueous solution, melamine and phytic acid as raw materials for hydrothermal reaction, and collecting precipitate after the reaction is finished, and freeze-drying to obtain a composite material precursor; and (3) placing the composite material precursor in an inert atmosphere for roasting to obtain the phosphate ion doped SnS crystal/nitrogen doped rGO composite material.
5. The method according to claim 4, wherein: the temperature of the hydrothermal reaction is 160-180 ℃ and the reaction time is 10-12 h.
6. The method according to claim 4, wherein: tin atoms in the tin salt, the sulfur source and the melamine: sulfur atom: the molar ratio of melamine is 2:2:5; the ratio of the phytic acid to the melamine is 0.5-2 mL to 5mol; the volume ratio of the phytic acid to the graphene oxide aqueous solution is 0.5-2:65, wherein the concentration of the graphene oxide aqueous solution is 2mg mL -1 。
7. The method according to claim 4, wherein: and placing the composite material precursor in a nitrogen or argon atmosphere, and roasting for 2-6 hours at 400-600 ℃ to obtain the phosphate ion doped SnS crystal/nitrogen doped rGO composite material.
8. The method according to claim 4, wherein: the tin salt is SnCl 4 ·5H 2 O or SnCl 2 The method comprises the steps of carrying out a first treatment on the surface of the The sulfur source is thiourea, thioacetamide or sodium sulfide.
9. Use of the phosphate ion doped SnS crystal/nitrogen doped rGO composite material according to any one of claims 1 to 3 as a negative electrode material for sodium ion batteries.
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