CN117142474A - Transition metal carbide-phosphide heterojunction @ C composite material and preparation and application thereof - Google Patents
Transition metal carbide-phosphide heterojunction @ C composite material and preparation and application thereof Download PDFInfo
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- CN117142474A CN117142474A CN202310848908.7A CN202310848908A CN117142474A CN 117142474 A CN117142474 A CN 117142474A CN 202310848908 A CN202310848908 A CN 202310848908A CN 117142474 A CN117142474 A CN 117142474A
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- 239000002131 composite material Substances 0.000 title claims abstract description 69
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 67
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 56
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 43
- 239000011593 sulfur Substances 0.000 claims abstract description 43
- 239000002243 precursor Substances 0.000 claims abstract description 39
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 20
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 10
- 239000011574 phosphorus Substances 0.000 claims abstract description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 15
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 14
- 238000005245 sintering Methods 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000006258 conductive agent Substances 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 150000003384 small molecules Chemical class 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- -1 polypyridine Polymers 0.000 claims description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims description 2
- 229960003638 dopamine Drugs 0.000 claims description 2
- 150000004679 hydroxides Chemical class 0.000 claims description 2
- 235000021317 phosphate Nutrition 0.000 claims description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 2
- 229920000767 polyaniline Polymers 0.000 claims description 2
- 229920001690 polydopamine Polymers 0.000 claims description 2
- 229920000128 polypyrrole Polymers 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims 1
- 229920001021 polysulfide Polymers 0.000 abstract description 13
- 239000005077 polysulfide Substances 0.000 abstract description 13
- 150000008117 polysulfides Polymers 0.000 abstract description 13
- 230000005764 inhibitory process Effects 0.000 abstract description 6
- 239000010405 anode material Substances 0.000 abstract description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 34
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 34
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 27
- 239000007774 positive electrode material Substances 0.000 description 24
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 23
- 239000011733 molybdenum Substances 0.000 description 23
- 239000002077 nanosphere Substances 0.000 description 23
- 238000010438 heat treatment Methods 0.000 description 22
- 239000002002 slurry Substances 0.000 description 20
- 229910052786 argon Inorganic materials 0.000 description 16
- 238000000197 pyrolysis Methods 0.000 description 16
- 239000010406 cathode material Substances 0.000 description 15
- 239000002033 PVDF binder Substances 0.000 description 13
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000011888 foil Substances 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- 239000003575 carbonaceous material Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 6
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- 230000006641 stabilisation Effects 0.000 description 6
- 238000011105 stabilization Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000011144 upstream manufacturing Methods 0.000 description 6
- 238000000498 ball milling Methods 0.000 description 5
- 239000012159 carrier gas Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- MEUZEBOPFDRIBW-UHFFFAOYSA-N ethanol;1h-pyrrole Chemical compound CCO.C=1C=CNC=1 MEUZEBOPFDRIBW-UHFFFAOYSA-N 0.000 description 5
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000013543 active substance Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000014233 sulfur utilization Effects 0.000 description 2
- 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 description 1
- 229910018091 Li 2 S Inorganic materials 0.000 description 1
- 241000219991 Lythraceae Species 0.000 description 1
- 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 description 1
- 235000014360 Punica granatum Nutrition 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000000875 high-speed ball milling Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 235000002949 phytic acid Nutrition 0.000 description 1
- 229940068041 phytic acid Drugs 0.000 description 1
- 239000000467 phytic acid Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
- C01B32/949—Tungsten or molybdenum carbides
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/08—Other phosphides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/90—Carbides
- C01B32/914—Carbides of single elements
-
- 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
- H01M10/052—Li-accumulators
-
- 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
-
- 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
- H01M4/5805—Phosphides
-
- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
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- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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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
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
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- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
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Abstract
The invention discloses a transition metal carbide-phosphide heterojunction @ C composite material, and preparation and application thereof. In the preparation process, a transition metal source and a carbon source are mixed to prepare a precursor material, and then the precursor material is sintered and heterogenized in a phosphorus source atmosphere, so that the composite material can be obtained. The material is applied to the preparation of lithium sulfur batteries, and is used as a lithium sulfur battery anode material, and the material has excellent sulfur carrying performance, polysulfide shuttle inhibition performance and electrochemical performance.
Description
Technical Field
The invention relates to the technical field of preparation of lithium ion battery anode materials, in particular to a transition metal carbide-phosphide heterojunction @ C composite material, and preparation and application thereof.
Background
Since the first advent of lithium sulfur battery technology in the 60 s of the last century, there has been interest in its potential. Although lithium ion batteries have high power density and high cycle stability and are widely applied to portable electronic products, electric automobiles and the like, the specific capacity of the positive electrode material of the lithium ion batteries is close to the theoretical specific capacity of the positive electrode material, the energy density of the lithium ion batteries is difficult to further increase, and the increase of the energy density by increasing the voltage platform of the positive electrode material brings about a safety problem. The positive electrode material is converted from a 'de-intercalation mechanism' to a 'conversion reaction chemical mechanism', so that the material with high specific capacity and specific energy can be obtained. Simple substance sulfur has the advantages of wide sources, abundant resources, low price, environmental friendliness and the like. Assuming complete conversion of sulfur to lithium sulfide (Li 2 S) and using metallic lithium as the negative electrode, the theoretical energy density of the lithium-sulfur battery is 2654 Wh.Kg -1 。
However, commercial development of lithium sulfur batteries has a number of technical problems, mainly low utilization of sulfur due to the insulation of elemental sulfur and lithium sulfide; the intermediate polysulfides are readily soluble in the electrolyte during charge and discharge, resulting in irreversible loss of active material and capacity fade. How to inhibit polysulfide diffusion, accelerate polysulfide conversion kinetics, and increase conductivity during sulfur positive electrode cycling is a key study of positive electrode materials.
To solve these problems of lithium-sulfur batteries, it is common to load elemental sulfur or polysulfide into a carbon-based material having high specific surface area, high porosity, and good conductivity characteristics to form a sulfur-containing composite cathode material. However, physically confining lithium polysulfide to pores of nonpolar carbon has proven effective only for medium-short term cycles, but long-term stability is not ideal.
Therefore, how to provide a new material to solve the above-mentioned drawbacks is a urgent problem for those skilled in the art.
Disclosure of Invention
Aiming at the problems of low sulfur load capacity, poor cycle performance and the like commonly existing in the lithium-sulfur battery positive electrode material in the prior art, the invention provides a transition metal carbide-phosphide heterojunction@C composite material which has excellent sulfur carrying performance, polysulfide shuttle inhibition performance and electrochemical performance.
In order to achieve the above purpose, the invention adopts the following technical scheme:
firstly, the invention provides a preparation method of a transition metal carbide-phosphide heterojunction @ C composite material, which comprises the following steps:
(1) Mixing a carbon source and a transition metal source to obtain a precursor material;
(2) And carrying out heterogeneous sintering on the precursor material in the atmosphere containing a phosphorus source to obtain the transition metal carbide-phosphide heterojunction @ C composite material.
The method is characterized in that a transition metal carbide and phosphide heterojunction thereof are formed by one-step heat treatment, the sulfur carrying efficiency and polysulfide shuttle inhibition performance of the prepared material are improved, the carbon source, the transition metal source and the phosphorus source are innovatively subjected to one-step heat treatment, and the combination control based on the component raw material proportion and the temperature is realized, so that the synergy can be realized, the one-step heterojunction of the transition metal carbide-phosphide can be realized in the industry for the first time, a carbon layer with a graphitized structure can be formed in situ, new materials with brand new phases and structures can be constructed, and more importantly, the material prepared by the preparation method has excellent polysulfide shuttle inhibition effect, and further has good conductivity, and excellent lithium sulfur battery capacity, multiplying power, energy density and cycle stability.
Preferably, the carbon source and the transition metal source in step (1) may be combined based on existing means, for example, the carbon source and the transition metal source may be mixed in a solid phase or a liquid phase to form the precursor.
Preferably, the step (1) specifically comprises: dispersing a transition metal source in deionized water, dispersing a carbon source in an alcohol organic compound, mixing and stirring the two at 20-50 ℃ for 10-20 h, and centrifuging/suction filtering to obtain a precursor material. Wherein the alcohol organic compound is preferably ethanol.
Preferably, the carbon source is one or more of a polymer, a non-polymeric monomer small molecule, and a small molecule monomer with polymerization capability.
Further, the polymer in the carbon source is one or more of polyaniline, polypyrrole, polypyridine and polydopamine, the small molecular monomer with polymerization capability is one or more of pyrrole, pyridine, aniline and dopamine, and the small molecular monomer with non-polymerization capability is small molecular sugar.
The precursor is constructed by adopting a small molecule in-situ polymerization method, which is favorable for further facilitating the construction of a subsequent carbide-phosphide heterojunction in one step and facilitating the electrochemical performance of a subsequent material.
Preferably, the transition metal source is one or more of oxides, hydroxides, organic acid salts, isopoly acid ammonium salts and phosphates of transition metals.
Preferably, the transition metal is one or more of Mo, V, mn.
Preferably, the phosphorus source is pH 3 Can be converted into PH 3 One or more of the precursor materials of (a).
In particular, said one capable of being converted into PH 3 The precursor material of (c) can be one or more of hypophosphite and phytic acid.
In the step (2), the carbon source and the transition metal source precursor are subjected to heterojunction roasting under the atmosphere containing a phosphorus source, specifically in the presence of PH 3 And (3) carrying out gas-solid heterojunction roasting treatment under the atmosphere of the catalyst. The atmosphere containing the phosphorus source in the gas-solid heterojunction roasting treatment can be directly introduced and contains PH 3 Atmosphere, or upstream, capable of being converted to pH 3 PH released by pyrolysis and gasification of precursor materials of (C) 3 An atmosphere. Through the gas-solid heterojunction, the combination control of the material proportion and the temperature is matched, the construction of the carbide-phosphide heterojunction in one step is facilitated, the shuttle inhibition effect of the prepared composite material on polysulfide is improved, and the electrochemical performance is facilitated.
Preferably, the mass ratio of the carbon source, the transition metal source and the phosphorus source is 1:5: (1-3).
Preferably, the sintering temperature in the step (2) is 650-850 ℃, and the sintering heat preservation time is 0.5-2 h.
Further, the temperature rising rate in the sintering stage is 3-10 ℃/min; more preferably 3 to 6 ℃/min.
The invention also claims a transition metal carbide-phosphide heterojunction @ C composite material prepared by the method according to the technical scheme.
The composite material integrally has a similar pomegranate structure from a macroscopic view, and heterojunction nano-particles are uniformly dispersed and coated in a carbon matrix. That is, the composite material takes a transition metal heterojunction as a core structure and is embedded in a graphitized carbon matrix shell structure. The material disclosed by the invention can realize synergy due to the control of the phase and the structure, is beneficial to fixing and inhibiting polysulfide, improving the electron conduction rate and improving the sulfur utilization rate of an active substance.
The invention also provides a transition metal carbide-phosphide heterojunction@C composite material prepared by the method and an application of the transition metal carbide-phosphide heterojunction@C composite material in preparing a lithium sulfur battery positive electrode, wherein the weight ratio of the transition metal carbide-phosphide heterojunction@C composite material to a sulfur source is (2): 8, compounding the materials in proportion to obtain the anode sulfur composite material.
Preferably, the sulfur source is elemental sulfur.
Preferably, the battery positive electrode further comprises a conductive agent and a binder, wherein the weight ratio of the positive electrode sulfur composite material to the conductive agent to the binder is 7:2:1. Wherein the conductive agent is conductive carbon black, and the binder is polyvinylidene fluoride.
The positive electrode may be prepared based on existing means, for example, the steps include:
1) Preparing a sulfur-carbon composite material:
mixing a transition metal carbide-phosphide heterojunction @ C composite material with a sulfur source through high-speed ball milling or hand milling, and performing heat treatment to fully compound the transition metal carbide-phosphide heterojunction @ C composite material and the sulfur source to obtain a sulfur-carbon composite material;
2) Preparing a positive electrode: and uniformly mixing the sulfur-carbon composite material, the conductive agent and the binder, dispersing the mixture in a proper amount of NMP to prepare slurry (the solid content is 70-90 wt%) and coating the slurry on an aluminum foil current collector, and carrying out vacuum drying to obtain the lithium-sulfur battery positive plate.
The invention also provides a lithium-sulfur battery, which comprises the lithium-sulfur battery anode according to the technical scheme.
Compared with the prior art, the invention discloses and provides a transition metal carbide-phosphide heterojunction @ C composite material, and preparation and application thereof, and has the following beneficial effects:
the invention provides a transition metal carbide-phosphide heterojunction @ C composite material, which is used as a sulfur-carrying material, and can improve the current-carrying capacity, the shuttle inhibition effect of polysulfide and the capacity, multiplying power, energy density and cycling stability of a lithium-sulfur battery.
The invention also provides a preparation method of the material, which can realize synergy through the joint control of the components, the proportion and the temperature, and can realize the construction of the carbon-coated carbide-phosphide heterojunction material in one step; furthermore, the electrochemical performance of the prepared material in a lithium-sulfur battery can be remarkably improved.
The method has the advantages of simple process, short flow and low cost. Is beneficial to industrialized production. The prepared thin-wall local graphitized porous carbon sphere/sulfur composite positive electrode material has high sulfur carrying capacity (the sulfur content is up to 80 wt.%), can effectively inhibit polysulfide from being dissolved in electrolyte, has high sulfur utilization rate of active substances and high specific capacity, and can greatly improve the cycle stability of a lithium-sulfur battery.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only embodiments of the present invention, and that other drawings can be obtained according to the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is an SEM image of a garnet-like transition metal molybdenum carbide-molybdenum phosphide heterojunction nanosphere/sulfur composite cathode material obtained in example 1;
FIG. 2 is an XRD pattern of the garnet-like transition metal molybdenum carbide-molybdenum phosphide heterojunction nanosphere/sulfur composite cathode material obtained in example 1;
FIG. 3 is a TEM image of the garnet-like transition metal molybdenum carbide-molybdenum phosphide heterojunction nanosphere/sulfur composite cathode material obtained in example 1;
FIG. 4 is a graph showing the first discharge of the garnet-like transition metal molybdenum carbide-molybdenum phosphide heterojunction nanosphere/sulfur composite cathode material obtained in example 1;
FIG. 5 is a graph showing 100 cycles of performance of the garnet-like transition metal molybdenum carbide-molybdenum phosphide heterojunction nanosphere/sulfur composite cathode material obtained in example 1 at a current density of 0.5C;
FIG. 6 is a graph showing the first discharge of the garnet-like transition metal molybdenum carbide-molybdenum phosphide heterojunction nanosphere/sulfur composite cathode material obtained in example 2;
FIG. 7 is a graph showing 100 cycles of performance of the obtained garnet-like transition metal molybdenum carbide-molybdenum phosphide heterojunction nanosphere/sulfur composite cathode material of example 2 at a current density of 0.5C;
FIG. 8 is a graph showing the first discharge of the garnet-like transition metal molybdenum carbide-molybdenum phosphide heterojunction nanosphere/sulfur composite cathode material obtained in example 3;
FIG. 9 is a graph showing 100 cycles of performance of the garnet-like transition metal molybdenum carbide-molybdenum phosphide heterojunction nanosphere/sulfur composite cathode material obtained in example 3 at a current density of 0.5C;
FIG. 10 is a graph showing the first discharge of the garnet-like transition metal molybdenum carbide-molybdenum phosphide heterojunction nanosphere/sulfur composite cathode material obtained in example 4;
FIG. 11 is a graph showing 100 cycles of performance of the obtained garnet-like transition metal molybdenum carbide-molybdenum phosphide heterojunction nanosphere/sulfur composite cathode material of example 4 at a current density of 0.5C;
FIG. 12 is a graph showing the first discharge of the garnet-like transition metal molybdenum carbide-molybdenum phosphide heterojunction nanosphere/sulfur composite cathode material obtained in example 5;
FIG. 13 is a graph showing 100 cycles of performance of the obtained garnet-like transition metal molybdenum carbide-molybdenum phosphide heterojunction nanosphere/sulfur composite cathode material of example 5 at a current density of 0.5C;
FIG. 14 is a graph showing the first discharge of the conductive carbon black/sulfur composite positive electrode material of comparative example 1;
fig. 15 is a graph of 100 cycles of the conductive carbon black/sulfur composite positive electrode material of comparative example 1 at a current density of 0.5C.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
(1) 4.38g phosphomolybdic acid was added to 200mL deionized water, 840. Mu.L pyrrole was added to 50mL absolute ethanol and dispersed ultrasonically. Slowly dripping the pyrrole ethanol solution into the phosphomolybdic acid water solution, stirring for 12 hours, and then carrying out suction filtration and drying to obtain a precursor material;
(2) Generating phosphine gas by thermally decomposing sodium hypophosphite in a hydrogen-argon mixed gas atmosphere, and mixing sodium hypophosphite with a precursor material according to the mass ratio of 1:3, placing the sodium hypophosphite in a tube furnace in an upstream mode, and placing a precursor sample in a downstream mode; heating sodium hypophosphite to pyrolysis volatilizing temperature, and releasing PH by pyrolysis 3 Contacting the precursor carried by carrier gas and downstream, and carrying out heterojunction heat treatment;
wherein the pyrolysis and volatilization temperature of the sodium hypophosphite is 350 ℃ (namely, the temperature of the sodium hypophosphite area is controlled to be 350 ℃), the heterojunction sintering temperature is 850 ℃ (the temperature of the precursor material setting area), and the heat preservation treatment time is 2 hours;
the obtained product is the garnet-like transition metal molybdenum carbide-molybdenum phosphide heterojunction nanosphere.
And (3) ball-milling and mixing the garnet-like transition metal molybdenum carbide-molybdenum phosphide heterojunction nanospheres and sulfur powder at a mass ratio of 2:8 for 2 hours, heating to 155 ℃ under the protection of argon, and preserving heat for 24 hours to obtain a grapheme-like carbon material/sulfur composite positive electrode material (composite positive electrode material), wherein an XRD (X-ray diffraction) diagram of the prepared material is shown in figure 1, an SEM (scanning electron microscope) diagram is shown in figure 2, and a TEM (electron microscope) diagram is shown in figure 3.
As can be seen from fig. 1-3, heterogeneous materials have been successfully prepared and sulfur is uniformly distributed throughout the composite cathode material.
The resulting composite positive electrode material, conductive carbon black, polyvinylidene fluoride (PVDF) was prepared according to 7:2:1, uniformly mixing the materials according to the mass ratio, dispersing the materials in NMP with a certain mass to prepare slurry (the solid content is 80 wt%) and then coating the slurry on an aluminum foil current collector, and vacuum drying the slurry at 60 ℃ to obtain the lithium-sulfur battery positive plate.
Battery assembly and testing: the positive electrode plate is punched into an electrode plate with the diameter of 14mm, a metal lithium plate is taken as a negative electrode, electrolyte is 1M LiTFSI/DOL: DME (1:1), and the CR2025 button cell is assembled in a glove box filled with argon. Constant current charge and discharge tests were carried out at room temperature (25 ℃) at a current density of 0.5C (837 mA/g), and the charge and discharge cut-off voltage was 1.7 to 2.8V.
As shown in fig. 4 and 5, the specific capacity of the first-turn discharge after stabilization was 1037mAh/g, and after 100 cycles, the specific capacity was 803mAh/g, and the capacity retention rates of 77.4% were respectively maintained.
Example 2
(1) 4.38g phosphomolybdic acid was added to 200mL deionized water, 840. Mu.L pyrrole was added to 50mL absolute ethanol and dispersed ultrasonically. Slowly dripping the pyrrole ethanol solution into the phosphomolybdic acid water solution, stirring for 12 hours, and then carrying out suction filtration and drying to obtain a precursor material;
(2) Generating phosphine gas by thermally decomposing sodium hypophosphite in a hydrogen-argon mixed gas atmosphere, and mixing sodium hypophosphite with a precursor material according to the mass ratio of 0.5:1, placing the sodium hypophosphite in a tube furnace, placing the sodium hypophosphite at the upstream, and placing the precursor sample at the downstream; heating sodium hypophosphite to pyrolysis volatilizing temperature, and releasing PH by pyrolysis 3 Contacting the precursor carried by carrier gas and downstream, and carrying out heterojunction heat treatment;
wherein the pyrolysis and volatilization temperature of the sodium hypophosphite is 350 ℃ (namely, the temperature of the sodium hypophosphite area is controlled to be 350 ℃), the heterojunction sintering temperature is 850 ℃ (the temperature of the precursor material setting area, the heating rate is 5 ℃/min), and the heat preservation treatment time is 2 hours;
the obtained product is the garnet-like transition metal molybdenum carbide-molybdenum phosphide heterojunction nanosphere.
And (3) ball-milling and mixing the garnet-like transition metal molybdenum carbide-molybdenum phosphide heterojunction nanospheres and sulfur powder at a mass ratio of 2:8 for 2 hours, heating to 155 ℃ under the protection of argon, and preserving heat for 24 hours to obtain a grapheme-like carbon material/sulfur composite positive electrode material (composite positive electrode material).
The resulting composite positive electrode material, conductive carbon black, polyvinylidene fluoride (PVDF) was prepared according to 7:2:1, uniformly mixing the materials according to the mass ratio, dispersing the materials in NMP with a certain mass to prepare slurry (the solid content is 80 wt%) and then coating the slurry on an aluminum foil current collector, and vacuum drying the slurry at 60 ℃ to obtain the lithium-sulfur battery positive plate.
Battery assembly and testing: the positive electrode plate is punched into an electrode plate with the diameter of 14mm, a metal lithium plate is taken as a negative electrode, electrolyte is 1M LiTFSI/DOL: DME (1:1), and the CR2025 button cell is assembled in a glove box filled with argon. Constant current charge and discharge tests were carried out at room temperature (25 ℃) at a current density of 0.5C (837 mA/g), and the charge and discharge cut-off voltage was 1.7 to 2.8V.
As shown in fig. 6 and 7, the specific capacity of the first-turn discharge after stabilization was 730mAh/g, and after 100 cycles, the specific capacity was 559mAh/g, and the capacity retention rates of 76.4% were maintained, respectively.
Example 3
(1) 4.38g phosphomolybdic acid was added to 200mL deionized water, 840. Mu.L pyrrole was added to 50mL absolute ethanol and dispersed ultrasonically. Slowly dripping the pyrrole ethanol solution into the phosphomolybdic acid water solution, stirring for 12 hours, and then carrying out suction filtration and drying to obtain a precursor material;
(2) Generating phosphine gas by thermally decomposing sodium hypophosphite in a hydrogen-argon mixed gas atmosphere, and mixing sodium hypophosphite with a precursor material according to a mass ratio of 1.5:1, placing the sodium hypophosphite in a tube furnace, placing the sodium hypophosphite at the upstream, and placing the precursor sample at the downstream; heating sodium hypophosphite to pyrolysis volatilizing temperature, and releasing PH by pyrolysis 3 Contacting the precursor carried by carrier gas and downstream, and carrying out heterojunction heat treatment;
wherein the pyrolysis and volatilization temperature of the sodium hypophosphite is 350 ℃ (namely, the temperature of the sodium hypophosphite area is controlled to be 350 ℃), the heterojunction sintering temperature is 850 ℃ (the temperature of the precursor material setting area, the heating rate is 5 ℃/min), and the heat preservation treatment time is 2 hours;
the obtained product is the garnet-like transition metal molybdenum carbide-molybdenum phosphide heterojunction nanosphere.
And (3) ball-milling and mixing the garnet-like transition metal molybdenum carbide-molybdenum phosphide heterojunction nanospheres and sulfur powder at a mass ratio of 2:8 for 2 hours, heating to 155 ℃ under the protection of argon, and preserving heat for 24 hours to obtain a grapheme-like carbon material/sulfur composite positive electrode material (composite positive electrode material).
The resulting composite positive electrode material, conductive carbon black, polyvinylidene fluoride (PVDF) was prepared according to 7:2:1, uniformly mixing the materials according to the mass ratio, dispersing the materials in NMP with a certain mass to prepare slurry (the solid content is 80 wt%) and then coating the slurry on an aluminum foil current collector, and vacuum drying the slurry at 60 ℃ to obtain the lithium-sulfur battery positive plate.
Battery assembly and testing: the positive electrode plate is punched into an electrode plate with the diameter of 14mm, a metal lithium plate is taken as a negative electrode, electrolyte is 1M LiTFSI/DOL: DME (1:1), and the CR2025 button cell is assembled in a glove box filled with argon. Constant current charge and discharge tests were carried out at room temperature (25 ℃) at a current density of 0.5C (837 mA/g), and the charge and discharge cut-off voltage was 1.7 to 2.8V.
As shown in fig. 8 and 9, the specific capacity of the first-turn discharge after stabilization was 921mAh/g, and after 100 cycles, the specific capacity was 763mAh/g, and the capacity retention rates of 82.8% were maintained, respectively.
Example 4
(1) 4.38g of phosphomolybdic acid was added to 200mL of deionized water, 340. Mu.L of pyrrole was added to 50mL of absolute ethanol and dispersed ultrasonically. Slowly dripping the pyrrole ethanol solution into the phosphomolybdic acid water solution, stirring for 12 hours, and then carrying out suction filtration and drying to obtain a precursor material;
(2) Generating phosphine gas by thermally decomposing sodium hypophosphite in a hydrogen-argon mixed gas atmosphere, and mixing sodium hypophosphite with a precursor material according to a mass ratio of 2:1, placing the sodium hypophosphite in a tube furnace, placing the sodium hypophosphite at the upstream, and placing the precursor sample at the downstream; heating sodium hypophosphite to pyrolysis volatilizing temperature, and releasing PH by pyrolysis 3 Contacting the precursor carried by carrier gas and downstream, and carrying out heterojunction heat treatment;
wherein the pyrolysis and volatilization temperature of the sodium hypophosphite is 350 ℃ (namely, the temperature of the sodium hypophosphite area is controlled to be 350 ℃), the heterojunction sintering temperature is 850 ℃ (the temperature of the precursor material setting area, the heating rate is 5 ℃/min), and the heat preservation treatment time is 2 hours;
the obtained product is the garnet-like transition metal molybdenum carbide-molybdenum phosphide heterojunction nanosphere.
And (3) ball-milling and mixing the garnet-like transition metal molybdenum carbide-molybdenum phosphide heterojunction nanospheres and sulfur powder at a mass ratio of 2:8 for 2 hours, heating to 155 ℃ under the protection of argon, and preserving heat for 24 hours to obtain a grapheme-like carbon material/sulfur composite positive electrode material (composite positive electrode material).
The resulting composite positive electrode material, conductive carbon black, polyvinylidene fluoride (PVDF) was prepared according to 7:2:1, uniformly mixing the materials according to the mass ratio, dispersing the materials in NMP with a certain mass to prepare slurry (the solid content is 80 wt%) and then coating the slurry on an aluminum foil current collector, and vacuum drying the slurry at 60 ℃ to obtain the lithium-sulfur battery positive plate.
Battery assembly and testing: the positive electrode plate is punched into an electrode plate with the diameter of 14mm, a metal lithium plate is taken as a negative electrode, electrolyte is 1M LiTFSI/DOL: DME (1:1), and the CR2025 button cell is assembled in a glove box filled with argon. Constant current charge and discharge tests were carried out at room temperature (25 ℃) at a current density of 0.5C (837 mA/g), and the charge and discharge cut-off voltage was 1.7 to 2.8V.
As shown in fig. 10 and 11, the initial discharge specific capacity after stabilization was 950mAh/g, and the specific capacity after 100 cycles was 780mAh/g, respectively, maintaining the capacity retention of 83.5%.
Example 5
(1) 1.38g of phosphomolybdic acid was added to 200mL of deionized water, 840. Mu.L of pyrrole was added to 50mL of absolute ethanol and dispersed ultrasonically. Slowly dripping the pyrrole ethanol solution into the phosphomolybdic acid water solution, stirring for 12 hours, and then carrying out suction filtration and drying to obtain a precursor material;
(2) Generating phosphine gas by thermally decomposing sodium hypophosphite in a hydrogen-argon mixed gas atmosphere, and mixing sodium hypophosphite with a precursor material according to the mass ratio of 0.8:1, placing the sodium hypophosphite in a tube furnace, placing the sodium hypophosphite at the upstream, and placing the precursor sample at the downstream; heating sodium hypophosphite to pyrolysis volatilizing temperature, and releasing PH by pyrolysis 3 Contacting the precursor carried by carrier gas and downstream, and carrying out heterojunction heat treatment;
wherein the pyrolysis and volatilization temperature of the sodium hypophosphite is 350 ℃ (namely, the temperature of the sodium hypophosphite area is controlled to be 350 ℃), the heterojunction sintering temperature is 850 ℃ (the temperature of the precursor material setting area, the heating rate is 5 ℃/min), and the heat preservation treatment time is 2 hours;
the obtained product is the garnet-like transition metal molybdenum carbide-molybdenum phosphide heterojunction nanosphere.
And (3) ball-milling and mixing the garnet-like transition metal molybdenum carbide-molybdenum phosphide heterojunction nanospheres and sulfur powder at a mass ratio of 2:8 for 2 hours, heating to 155 ℃ under the protection of argon, and preserving heat for 24 hours to obtain a grapheme-like carbon material/sulfur composite positive electrode material (composite positive electrode material).
The resulting composite positive electrode material, conductive carbon black, polyvinylidene fluoride (PVDF) was prepared according to 7:2:1, uniformly mixing the materials according to the mass ratio, dispersing the materials in NMP with a certain mass to prepare slurry (the solid content is 80 wt%) and then coating the slurry on an aluminum foil current collector, and vacuum drying the slurry at 60 ℃ to obtain the lithium-sulfur battery positive plate.
Battery assembly and testing: the positive electrode plate is punched into an electrode plate with the diameter of 14mm, a metal lithium plate is taken as a negative electrode, electrolyte is 1M LiTFSI/DOL: DME (1:1), and the CR2025 button cell is assembled in a glove box filled with argon. Constant current charge and discharge tests were carried out at room temperature (25 ℃) at a current density of 0.5C (837 mA/g), and the charge and discharge cut-off voltage was 1.7 to 2.8V.
As shown in fig. 12 and 13, the specific capacity of the first-turn discharge after stabilization was 900mAh/g, and after 100 cycles, the specific capacity was maintained at 700mAh/g, respectively, maintaining 80% capacity retention.
Comparative example 1
Sulfur, conductive carbon black, polyvinylidene fluoride (PVDF) according to 7:2:1, uniformly mixing the materials according to the mass ratio, dispersing the materials in NMP with a certain mass to prepare slurry (the solid content is 80 wt%) and then coating the slurry on an aluminum foil current collector, and vacuum drying the slurry at 60 ℃ to obtain the lithium-sulfur battery positive plate.
The battery assembly and test were: the positive electrode plate is punched into an electrode plate with the diameter of 14mm, a metal lithium plate is taken as a negative electrode, electrolyte is 1M LiTFSI/DOL: DME (1:1), and the CR2025 button cell is assembled in a glove box filled with argon. Constant current charge and discharge tests were carried out at room temperature (25 ℃) at a current density of 0.5C (837 mA/g), and the charge and discharge cut-off voltage was 1.7 to 2.8V.
As shown in fig. 14 and 15, the specific capacity of the first-turn discharge after stabilization was 500mAh/g, and after 100 cycles, the specific capacity was maintained at 400mAh/g, respectively, maintaining 80% capacity retention.
In the present specification, each embodiment is described in a progressive manner, and each embodiment is mainly described in a different point from other embodiments, and identical and similar parts between the embodiments are all enough to refer to each other. For the device disclosed in the embodiment, since it corresponds to the method disclosed in the embodiment, the description is relatively simple, and the relevant points refer to the description of the method section.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The preparation method of the transition metal carbide-phosphide heterojunction @ C composite material is characterized by comprising the following steps of:
(1) Mixing a carbon source and a transition metal source to obtain a precursor material;
(2) And carrying out heterogeneous sintering on the precursor material in the atmosphere containing a phosphorus source to obtain the transition metal carbide-phosphide heterojunction @ C composite material.
2. The method for preparing a transition metal carbide-phosphide heterojunction @ C composite material as claimed in claim 1, wherein said carbon source is one or more of a polymer, a non-polymeric monomer small molecule, and a small molecule monomer having a polymerization ability.
3. The method for preparing a transition metal carbide-phosphide heterojunction @ C composite material as claimed in claim 1 or 2, wherein said carbon source is one or more of polyaniline, polypyrrole, polypyridine, polydopamine, pyrrole, pyridine, aniline, dopamine and small-molecule sugar.
4. The method for preparing a transition metal carbide-phosphide heterojunction @ C composite material as claimed in claim 1, wherein the transition metal source is one or more of oxides, hydroxides, organic acid salts, isopoly acid ammonium salts and phosphates of transition metals, and the transition metals are one or more of Mo, V and Mn.
5. The method for preparing a transition metal carbide-phosphide heterojunction @ C composite material as claimed in claim 1, wherein said phosphorus source is PH 3 Can be converted into PH 3 One or more of the precursor materials of (a).
6. The method for preparing a transition metal carbide-phosphide heterojunction @ C composite material as claimed in claim 1, wherein the mass ratio of the carbon source, the transition metal source and the phosphorus source is 1:5: (1-3).
7. The method for preparing a transition metal carbide-phosphide heterojunction @ C composite material as claimed in claim 1, wherein the sintering temperature in the step (2) is 650-850 ℃, and the sintering heat-preserving time is 0.5-2 h.
8. Use of the transition metal carbide-phosphide heterojunction @ C composite material prepared by the method of any one of claims 1-7 in preparing a positive electrode of a lithium-sulfur battery, wherein the weight ratio of the transition metal carbide-phosphide heterojunction @ C composite material to a sulfur source is (2): 8, compounding the materials in proportion to obtain the anode sulfur composite material.
9. The use according to claim 8, wherein the positive electrode of the lithium-sulfur battery further comprises a conductive agent and a binder, the weight ratio of the positive electrode sulfur composite material, the conductive agent and the binder being 7:2:1.
10. A lithium sulfur battery comprising the positive electrode of the lithium sulfur battery of claim 9.
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