CN114242984B - Preparation method of layered iron-cobalt phosphide/carbon composite material and button cell - Google Patents
Preparation method of layered iron-cobalt phosphide/carbon composite material and button cell Download PDFInfo
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- CN114242984B CN114242984B CN202111563183.4A CN202111563183A CN114242984B CN 114242984 B CN114242984 B CN 114242984B CN 202111563183 A CN202111563183 A CN 202111563183A CN 114242984 B CN114242984 B CN 114242984B
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- 239000002131 composite material Substances 0.000 title claims abstract description 56
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- QVYYOKWPCQYKEY-UHFFFAOYSA-N [Fe].[Co] Chemical compound [Fe].[Co] QVYYOKWPCQYKEY-UHFFFAOYSA-N 0.000 title claims abstract description 33
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 44
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 24
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000012429 reaction media Substances 0.000 claims abstract description 23
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 20
- 238000005406 washing Methods 0.000 claims abstract description 20
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 17
- 239000010941 cobalt Substances 0.000 claims abstract description 17
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 239000002738 chelating agent Substances 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 229910052742 iron Inorganic materials 0.000 claims abstract description 12
- 229910052786 argon Inorganic materials 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 8
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims abstract description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 5
- 239000012716 precipitator Substances 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 54
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 36
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 239000008367 deionised water Substances 0.000 claims description 26
- 229910021641 deionized water Inorganic materials 0.000 claims description 26
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 17
- 238000001291 vacuum drying Methods 0.000 claims description 17
- 239000002033 PVDF binder Substances 0.000 claims description 16
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 14
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 239000006230 acetylene black Substances 0.000 claims description 10
- 239000006258 conductive agent Substances 0.000 claims description 10
- 239000011889 copper foil Substances 0.000 claims description 10
- 239000011268 mixed slurry Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 claims description 8
- 239000013543 active substance Substances 0.000 claims description 8
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 7
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical group O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 239000002932 luster Substances 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 5
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 4
- 229910017061 Fe Co Inorganic materials 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 claims description 4
- 229960001826 dimethylphthalate Drugs 0.000 claims description 4
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 4
- 239000011790 ferrous sulphate Substances 0.000 claims description 4
- 238000003837 high-temperature calcination Methods 0.000 claims description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 4
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 3
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 3
- 235000019800 disodium phosphate Nutrition 0.000 claims description 3
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 claims description 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 3
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 2
- 229910013870 LiPF 6 Inorganic materials 0.000 claims 1
- 239000007772 electrode material Substances 0.000 abstract description 9
- 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 abstract 1
- 229910052708 sodium Inorganic materials 0.000 abstract 1
- 239000011734 sodium Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 13
- 238000001816 cooling Methods 0.000 description 8
- 229910052593 corundum Inorganic materials 0.000 description 8
- 239000010431 corundum Substances 0.000 description 8
- 239000011267 electrode slurry Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 229910013872 LiPF Inorganic materials 0.000 description 6
- 101150058243 Lipf gene Proteins 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000013384 organic framework Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Images
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
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- Battery Electrode And Active Subsutance (AREA)
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Abstract
The invention relates to a preparation method of a layered structure iron-cobalt phosphide/carbon composite material and a button cell, belongs to the technical field of electrode material preparation, and solves the problem that in the prior art, the electrochemical performance of a phosphide metal serving as an electrode material is poor. The method comprises the following steps: (1) Dissolving an iron source and a precipitator in a first reaction medium, stirring, transferring the obtained mixture into a high-pressure reaction kettle liner, and preserving heat for reaction; centrifuging, washing and drying the product to obtain an iron oxide micron rod; (2) Taking the ferric oxide micron rod obtained in the step (1) as a template, taking cobalt nitrate and/or cobalt chloride as a cobalt source, simultaneously adding a chelating agent, mixing the template, the cobalt source, the chelating agent and a second reaction medium, performing ultrasonic dispersion for 10-12min, stirring, centrifuging, washing and drying an obtained product, adding sodium hydrophosphate into an argon gas stream, and calcining at a high temperature. The prepared composite material has better electrochemical performance.
Description
Technical Field
The invention relates to the technical field of preparation of new energy electrode materials, in particular to a preparation method of a layered structure iron-cobalt phosphide/carbon composite material and a button cell.
Background
Transition metal phosphide has many advantages as a lithium ion battery anode material, and most researches show that the phosphide material has a specific capacity higher than that of a commercial graphite electrode (372 mAh/g). However, the capacity fade during cycling is large due to the aggregation of particles during electrochemical reaction and the large volume change during charge and discharge cycling; furthermore, the formation of a solid electrolyte layer (SEI) during charge and discharge can also result in capacity loss, limiting further applications of phosphide electrode materials.
Disclosure of Invention
In view of the above analysis, the present invention aims to provide a method for preparing a layered iron-cobalt phosphide/carbon composite material and a button cell, which are used for solving the problems of large capacity attenuation in the cycle process of taking the existing phosphide metal as an electrode material and capacity loss in the charge-discharge process.
The invention provides a preparation method of a layered structure iron-cobalt phosphide/carbon composite material, which comprises the following steps:
(1) Preparation of ferric oxide micron rods: dissolving an iron source and a precipitator in a first reaction medium, stirring, transferring the obtained mixture into a high-pressure reaction kettle liner, and preserving heat for reaction; centrifuging, washing and drying the product after the reaction is finished to obtain an iron oxide micron rod;
(2) Preparation of iron cobalt phosphide/carbon composite material: taking the ferric oxide micron rod obtained in the step (1) as a template, taking cobalt nitrate and/or cobalt chloride as a cobalt source, simultaneously adding a chelating agent, mixing the template, the cobalt source, the chelating agent and a second reaction medium, performing ultrasonic dispersion for 10-12min, stirring, centrifuging, washing and drying the obtained product to obtain the ferric oxide micron rod Fe with an organic framework structure containing metallic cobalt 2 O 3 @Co-MOF; in argon flow, fe 2 O 3 Mixing the @ Co-MOF and sodium hydrogen phosphate, and calcining at high temperature to obtain the Fe-Co phosphide/carbon composite material FeP@CoP/C.
Preferably, in step (1), the ratio of the amount of the iron source, the precipitant and the first reaction medium is: 10-13mmol:5-13mmol:70-75mL.
Preferably, the iron source is one or more of ferric chloride, ferrous sulfate and ferric nitrate; the precipitant is one or more of oxalic acid, propylene diamine, sodium thiosulfate, sodium bicarbonate, sodium carbonate and ammonia water; the first reaction medium is a deionized water mixed solution containing at least two of glycerol, ethylene glycol, ethanol, methanol and dimethyl phthalate.
Preferably, in step (1), the reaction temperature is 160-220 ℃ and the reaction time is 4-16h.
Preferably, in the step (2), the dosage ratio of the ferric oxide micron rod, the cobalt source, the chelating agent and the second reaction medium is 0.2-0.4g:0.1-0.2g:1-2g:70-75mL.
Preferably, in step (2), fe 2 O 3 The dosage ratio of the @ Co-MOF to the sodium hydrogen hypophosphite is 0.1-0.3g:1-3g.
Preferably, the second reaction medium is a deionized water mixed solution containing at least two of methanol, ethanol, ethylene glycol and glycerol.
Preferably, the chelating agent is one or more of cetyltrimethylammonium bromide, sodium dodecylbenzenesulfonate, polyvinylpyrrolidone, 2-methylimidazole.
Preferably, in the step (2), the flow rate of the argon gas flow is 25-80mL/min, and the high-temperature calcination process comprises the following steps: the calcination temperature is 300-550 ℃, the temperature rising rate is 2-5 ℃/min, and the time is 2-3h.
In another aspect, the invention provides a button cell, the negative electrode of which comprises the iron-cobalt phosphide/carbon composite material obtained by the preparation method of the invention, and a metal lithium sheet is used as a counter electrode and a reference electrode.
Preferably, the negative electrode further comprises a conductive agent acetylene black and a binder polyvinylidene fluoride PVDF; the negative electrode is prepared by the following method: taking N-methyl pyrrolidone NMP as a solvent, and mixing active substances of iron cobalt phosphide/carbon composite material, conductive agent acetylene black and binder polyvinylidene fluoride PVDF according to the dosage ratio of 320-340mg:40-50mg: and (3) uniformly mixing 40-50mg until the mixed slurry has metallic luster, uniformly coating the prepared mixed slurry on the copper foil, vacuum drying at 60-70 ℃ for 12-14h, taking out, and stamping to obtain the pole piece.
Preferably, the copper foil has a size of 6cm multiplied by 7cm, and the punched pole piece has a diameter of 8-9mm.
Preferably, the electrolyte of the button cell is LiPF with the concentration of 1.0mol/L 6 The solvent is ethylene carbonate, dimethyl carbonate and diethyl carbonate according to the weight ratio of 1:1:1 by volume of the mixture.
Preferably, the button cell is composed in a glove box having a water oxygen content of less than 0.01ppm.
Compared with the prior art, the invention has at least one of the following beneficial effects:
1. the preparation method is simple, efficient and convenient; and the prepared iron-cobalt phosphide/carbon composite material (FeP@CoP/C) has a multi-stage layered structure, higher conductivity and excellent electrochemical performance.
2. The invention firstly proposes the use of ferric oxide (Fe 2 O 3 ) The bimetal phosphide composite material is prepared for the template, and a brand new idea is provided for the phosphide serving as the negative electrode material of the lithium ion battery.
3. The Fe-Co phosphide/carbon composite material FeP@CoP/C obtained by the preparation method is used as a negative electrode material of a lithium ion battery, and is assembled into a button battery for electrochemical performance test, and the button battery has a first-week discharge specific capacity of 400mAh/g under a current density of 200 mA/g.
In the invention, the technical schemes can be mutually combined to realize more preferable combination schemes. Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention may be realized and attained by the structure particularly pointed out in the written description and drawings.
Drawings
The drawings are only for purposes of illustrating particular embodiments and are not to be construed as limiting the invention, like reference numerals being used to refer to like parts throughout the several views.
FIG. 1 is an SEM image of FeP@CoP/C prepared in example 1.
FIG. 2 is an XRD pattern for FeP@CoP/C prepared in example 1.
Fig. 3 is a charge-discharge curve of the battery of example 1 using fep@cop/C as an electrode material.
FIG. 4 is a cycle chart of a battery of example 1 having FeP@CoP/C as an electrode material.
Fig. 5 is a graph showing the rate performance of the battery of example 1 using fep@cop/C as an electrode material.
Detailed Description
Preferred embodiments of the present invention will now be described in detail with reference to the accompanying drawings, which form a part hereof, and together with the description serve to explain the principles of the invention, and are not intended to limit the scope of the invention.
The solution for improving the electrochemical performance of the metal phosphide can be to reasonably design the phase and morphology of the phosphide electrode material, so that the unique advantages of the material can be exerted, and the defects of the material can be weakened and improved.
The composite of the phosphide and the functional carbon material is also an effective method for improving the electrochemical performance of the phosphide, firstly, the carbon material has conductivity, so that the electron transmission can be enhanced, and the conductivity of the material is improved; and secondly, the carbon material can construct a complex shape and is endowed with a large number of pore canals, so that the effects of preventing active substances from gathering and relieving volume change are achieved.
Thus, the invention provides a preparation method of a layered structure iron-cobalt phosphide/carbon composite material, which comprises the following steps:
(1) Preparation of ferric oxide micron rods:
dissolving an iron source and a precipitator in a first reaction medium, stirring, transferring the obtained mixture into a high-pressure reaction kettle liner, and preserving heat for reaction; centrifuging, washing and drying the product after the reaction is finished to obtain an iron oxide micron rod;
(2) Preparation of iron cobalt phosphide/carbon composite material:
taking the ferric oxide micron rod obtained in the step (1) as a template, taking cobalt nitrate and/or cobalt chloride as a cobalt source, simultaneously adding a chelating agent, mixing the template, the cobalt source, the chelating agent and a second reaction medium, performing ultrasonic dispersion for 10-12min, stirring, centrifuging, washing and drying the obtained product to obtain the ferric oxide micron rod Fe with an organic framework structure containing metallic cobalt 2 O 3 @Co-MOF; in argon flow, fe 2 O 3 Mixing the @ Co-MOF and sodium hydrogen phosphate, and calcining at high temperature to obtain the Fe-Co phosphide/carbon composite material FeP@CoP/C.
The invention adopts the iron source and the precipitator to be mixed and reacted in a high-pressure reaction kettleObtaining ferric oxide micron rods, then taking the ferric oxide micron rods as templates, and carrying out hydrothermal reaction on the ferric oxide micron rods and a cobalt source in the presence of a chelating agent to generate a cobalt-containing metal organic framework Fe 2 O 3 And (3) carrying out high-temperature phosphating on the obtained product to obtain the iron-cobalt phosphide/carbon composite material.
The product obtained by the invention is a multi-level layered iron-cobalt phosphide/carbon composite material formed by stacking one-dimensional micron rods, and the structure has larger specific surface area, larger reaction interface, controllable morphology and function, and proper carbon coating can effectively increase the conductivity of the material and buffer the volume change of the active material in the charge-discharge process. Compared with the prior art, the iron-cobalt phosphide/carbon composite material obtained by the preparation method has the characteristics of high conductivity, long cycle life, environmental protection, simple preparation and excellent performance.
In the present invention, preferably, in the step (1), the iron source, the precipitant and the first reaction medium are used in the following ratio: 10-13mmol:5-13mmol:70-75mL, such as 10mmol:7mmol:70mL, 10mmol:10mmol:70mL, 10mmol:5mmol:70mL, 11mmol:10mmol:70mL, 10mmol:13mmol:75mL, 10mmol:12mmol:70mL, 13mmol:13mmol:75mL, 13mmol:13mmol:70mL, 10-13mmol:10-13mmol:70-75mL.
Further preferably, the iron source is one or more of ferric chloride, ferrous sulfate and ferric nitrate; the precipitant is one or more of oxalic acid, propylene diamine, sodium thiosulfate, sodium bicarbonate, sodium carbonate and ammonia water; the first reaction medium is a deionized water mixed solution containing at least two of glycerol, ethylene glycol, ethanol, methanol and dimethyl phthalate.
Further preferably, the ratio of the amount of glycerol, ethylene glycol, ethanol, methanol and dimethyl phthalate to the amount of deionized water in the first reaction medium is 40-60mL:10-30mL, such as 40mL:30mL, 50mL:20mL, 60mL:10mL.
In the invention, the specific iron source, the precipitant, the first reaction medium and the specific dosage are adopted to ensure that the prepared product has better electrochemical performance. Further toPreferably, the ferric chloride is FeCl 3 ·6H 2 O, ferrous sulfate is FeSO 4 ·7H 2 O, ferric nitrate is Fe (NO) 3 ) 2 ·9H 2 O。
Illustratively, in step (1), the stirring is performed in a rotor stirrer at a rotational speed of 160-240r/min, such as 160r/min, 180r/min, 200r/min, 220r/min, 240r/min; the stirring time is 10-20min, such as 10min, 12min, 15min, 18min, and 20min.
In order to further improve the electrochemical performance of the iron-cobalt phosphide/carbon composite material, in the step (1), the reaction temperature is 160-220 ℃, such as 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃ and 220 ℃; the reaction time is 4-16h, such as 4h, 6h, 8h, 10h, 12h, 14h, 16h. Further preferably, the volume of the autoclave liner is 100-110mL.
Specifically, in the step (1), the centrifugation process is carried out in a centrifuge, and the rotating speed of the centrifuge is 7800-8000r/min; the washing process includes: washing 3 times with deionized water and 2 times with ethanol; the drying process comprises the following steps: drying in vacuum drying oven at 80-90deg.C (such as 80deg.C and 85deg.C) for 12-14 hr.
In the invention, the iron oxide micron rod prepared in the step (1) is used as a raw material to prepare the iron cobalt phosphide/carbon composite material, preferably, in the step (2), the dosage ratio of the iron oxide micron rod, the cobalt source, the chelating agent and the second reaction medium is 0.2-0.4g:0.1-0.2g:1-2g:70-75mL, such as 0.4g:0.1g:1.8g:70mL, 0.3g:0.1g:1g:70mL, 0.2g:0.1g:1g:70mL, 0.2g:0.1g:1g:75mL, 0.4g:0.1g:1g:70mL, 0.4g:0.2g:1g:75mL.
Further preferably, in step (2), fe 2 O 3 The dosage ratio of the @ Co-MOF to the sodium hydrogen hypophosphite is 0.1-0.3g:1-3g, such as 0.3g:3g, 0.2g:1.8g, 0.1g:1g, 0.2g:2g, 0.3g:1g. The prepared iron-cobalt phosphide/carbon composite material FeP@CoP/C has a multi-stage layered structure, higher conductivity and excellent electrochemical performance.
In the present invention, preferably, the cobalt nitrate is Co (NO 3 ) 2 ·6H 2 O, cobalt chloride isCoCl 2 ·6H 2 O。
In the present invention, the second reaction medium is preferably a deionized water mixed solution containing at least two of methanol, ethanol, ethylene glycol and glycerol. Further preferably, the ratio of the total amount of methanol, ethanol, ethylene glycol, glycerol to deionized water in the second reaction medium is 50-60mL:10-20mL. The chelating agent is preferably one or more of cetyltrimethylammonium bromide (CTAB), sodium dodecylbenzene sulfonate (SDBS), polyvinylpyrrolidone (PVP), and 2-methylimidazole.
Specifically, in the step (2), the stirring process is performed in a rotor stirrer, the rotating speed is 200-220r/min, and the stirring time is 3-10h.
Illustratively, in step (2), the centrifugation is performed in a centrifuge at a rotational speed of 7800-7900r/min; the washing process comprises the following steps: washing 3 times with deionized water and 2 times with ethanol; the drying process comprises the following steps: drying in a vacuum drying oven at 80-90 ℃ for 12-14h to obtain the ferric oxide micron rod Fe with the organic framework structure containing metallic cobalt 2 O 3 @Co-MOF。
Further preferably, in step (2), the flow rate of the argon gas flow is 25-80mL/min, such as 25mL/min, 30mL/min, 35mL/min, 40mL/min, 45mL/min, 50mL/min, 55mL/min, 60mL/min, 65mL/min, 70mL/min, 75mL/min, 80mL/min; the high temperature calcination process comprises: the calcination temperature is 300-550deg.C, such as 300 deg.C, 350 deg.C, 400 deg.C, 450 deg.C, 500 deg.C, 550 deg.C; the heating rate is 2-5deg.C/min, such as 2deg.C/min, 2.5deg.C/min, 3deg.C/min, 3.5deg.C/min, 4deg.C/min, 4.5deg.C/min, and 5deg.C/min; the time is 2-3h. Further preferably, the process of high temperature calcination comprises: heating to 300-350 ℃ at a heating rate of 2-3 ℃/min, preserving heat for 2-3h, heating to 500-550 ℃ at a heating rate of 4-5 ℃/min, and preserving heat for 2-3h.
On the other hand, the invention also provides a button cell, and the negative electrode of the button cell comprises the iron-cobalt phosphide/carbon composite material obtained by the preparation method, and a metal lithium sheet is used as a counter electrode and a reference electrode.
Specifically, the negative electrode further comprises a conductive agent acetylene black and a binder polyvinylidene fluoride PVDF; the negative electrode is prepared by the following method: taking N-methyl pyrrolidone NMP as a solvent, and mixing active substances of iron cobalt phosphide/carbon composite material, conductive agent acetylene black and binder polyvinylidene fluoride PVDF according to the dosage ratio of 320-340mg:40-50mg: mixing 40-50mg, such as 320mg:40mg:40mg, 320mg:50mg:50mg, 340mg:40mg:40mg, 340mg:50mg:50mg, 340mg:40mg:50mg, 330mg:45mg:45mg, 330mg:40mg:40mg, 330mg:50mg:50mg; and (3) until the mixed slurry has metallic luster, uniformly coating the prepared mixed slurry on the copper foil, vacuum drying at 60-70 ℃ for 12-14 hours, taking out, and stamping to obtain the pole piece.
Further preferably, the copper foil has a size of 6cm×7cm, and the punched pole piece has a diameter of 8-9mm.
Illustratively, the electrolyte of the button cell is LiPF of 1.0mol/L 6 The solvent is ethylene carbonate, dimethyl carbonate and diethyl carbonate according to the weight ratio of 1:1:1 by volume of the mixture. Further preferably, the button cell is composed in a glove box having a water oxygen content of less than 0.01ppm.
The method for preparing the layered structure iron-cobalt phosphide/carbon composite material and button cell of the present invention are further described below by way of specific examples.
Example 1
(1) Preparation of ferric oxide micron rod
2.7g of FeCl was weighed out separately by a balance 3 ·6H 2 O,0.9g of oxalic acid, was transferred into a beaker having a volume of 100mL, followed by adding 30mL of deionized water, 20mL of glycerol, and 20mL of ethylene glycol, and magnetically stirring at a rotation speed of 160r/min for 20min. The mixture was then transferred to a 100mL reactor liner and reacted at 160℃for 12h. Standing the reaction kettle after the reaction is finished, removing upper liquid, centrifugally washing with deionized water for 3 times and ethanol for 2 times at the rotating speed of 7800r/min by using a centrifuge, and then drying in a vacuum drying oven at 80 ℃ for 12 hours to obtain ferric oxide micron rods;
(2) Preparation of iron cobalt phosphide/carbon composite FeP@CoP/C
0.4g of iron oxide micron rods and 0.1g of Co (NO) were weighed out by a balance 3 ) 2 ·6H 2 O,1g PVP. This was transferred to a beaker having a volume of 100mL, followed by adding 10mL of deionized water, 40mL of methanol, 20mL of ethanol, and after ultrasonic dispersion for 10min, magnetically stirring at a rotational speed of 200r/min for 6h. After the reaction is finished, removing upper liquid, centrifugally washing with deionized water for 3 times at the rotating speed of 7800r/min by using a centrifugal machine, and then drying in a vacuum drying oven at 80 ℃ for 12 hours to obtain a product Fe 2 O 3 @Co-MOF; taking 0.2g of product Fe 2 O 3 The @ Co-MOF was placed in the updraft of a corundum ark, 1.8g NaH was taken 2 PO 2 Placing the mixture into the lower air flow of a corundum ark, setting the heating rate to be 2 ℃/min in the argon air flow with the flow rate of 25mL/min, and preserving the heat for 3h when the temperature rises to 300 ℃. And then, setting the heating rate to 5 ℃/min, calcining at a high temperature of 550 ℃ for 2 hours, and slowly cooling to room temperature along with furnace cooling to obtain the iron-cobalt phosphide/carbon composite material FeP@CoP/C. FIGS. 1 and 2 are SEM and XRD patterns of FeP@CoP/C, respectively; it can be seen from the figure that there are multiple levels of hierarchy.
(3) Preparation of button cell
Assembling the FeP@CoP/C composite material prepared in the step (2) into an electrode, wherein the electrode comprises the following concrete steps: 320mg of active substance FeP@CoP/C composite material, 40mg of conductive agent acetylene black and 40mg of PVDF are uniformly mixed, NMP is used as a solvent and uniformly mixed until the mixed slurry has metallic luster, the prepared electrode slurry is uniformly coated on a copper foil with the thickness of 6cm multiplied by 7cm, and the electrode slurry is taken out after vacuum drying for 12 hours at the temperature of 60 ℃ and punched into a pole piece with the diameter of 8 mm.
The prepared pole piece containing FeP@CoP/C composite material is used as a negative electrode of a battery, a metal lithium sheet is used as a counter electrode and a reference electrode, and an electrolyte is LiPF with the concentration of 1.0mol/L 6 The solvent is ethylene carbonate, dimethyl carbonate and diethyl carbonate according to the weight ratio of 1:1:1, and the button cell is formed in a glove box with water oxygen content lower than 0.01ppm.
(4) Electrochemical performance detection
The battery was cycled and rate performance tested between 0.1-3V using a blue charge and discharge tester. The results are shown in FIGS. 3-5.
As can be seen from fig. 3 to 5, the battery using the FeP@CoP/C composite material obtained by the preparation method provided by the invention as a negative electrode has good charge and discharge performance, cycle performance and rate capability.
Example 2
(1) Preparation of ferric oxide micron rod
2.78g of FeSO was weighed out by a balance 4 ·7H 2 O,0.84g NaHCO 3 . This was transferred to a 100mL beaker, followed by the addition of 20mL deionized water, 20mL DMP, 30mL ethanol, and magnetic stirring at 200r/min for 15min. The mixture was then transferred to a 100mL reactor liner and reacted at 180℃for 8h. Standing the reaction kettle after the reaction is finished, removing upper liquid, centrifugally washing with deionized water for 3 times and ethanol for 2 times at the rotating speed of 7800r/min by using a centrifuge, and then drying in a vacuum drying oven at 80 ℃ for 12 hours to obtain ferric oxide micron rods;
(2) Preparation of iron cobalt phosphide/carbon composite FeP@CoP/C
0.3g of ferric oxide micron rods and 0.1g of CoCl are respectively weighed by a balance 2 ·6H 2 O,1g of 2-methylimidazole. This was transferred to a beaker having a volume of 100mL, followed by adding 20mL of deionized water, 30mL of methanol, 20mL of ethylene glycol, and after ultrasonic dispersion for 10min, magnetically stirring for 3h at a rotational speed of 200 r/min. After the reaction is finished, removing upper liquid, centrifugally washing with deionized water for 3 times at the rotating speed of 7800r/min by using a centrifugal machine, and then drying in a vacuum drying oven at 80 ℃ for 12 hours to obtain a product Fe 2 O 3 @Co-MOF; taking 0.1g of product Fe 2 O 3 Placing @ Co-MOF in the updraft of corundum ark, taking 1g of NaH 2 PO 2 Placing the mixture into the lower air flow of a corundum ark, setting the heating rate to be 3 ℃/min in the argon air flow with the flow rate of 50mL/min, and preserving the heat for 2h when the temperature rises to 350 ℃. And then, setting the heating rate to be 4 ℃/min, calcining at a high temperature of 500 ℃ for 3 hours, and slowly cooling to room temperature along with furnace cooling to obtain the iron-cobalt phosphide/carbon composite material FeP@CoP/C.
(3) Preparation of button cell
Assembling the FeP@CoP/C composite material prepared in the step (2) into an electrode, wherein the electrode comprises the following concrete steps: 320mg of active substance FeP@CoP/C composite material, 40mg of conductive agent acetylene black and 40mg of PVDF are uniformly mixed, NMP is used as a solvent and uniformly mixed until the mixed slurry has metallic luster, the prepared electrode slurry is uniformly coated on a copper foil with the thickness of 6cm multiplied by 7cm, and the electrode slurry is taken out after vacuum drying for 12 hours at the temperature of 60 ℃ and punched into a pole piece with the diameter of 8 mm.
The prepared pole piece containing FeP@CoP/C composite material is used as a negative electrode of a battery, a metal lithium sheet is used as a counter electrode and a reference electrode, and an electrolyte is LiPF with the concentration of 1.0mol/L 6 The solvent is ethylene carbonate, dimethyl carbonate and diethyl carbonate according to the weight ratio of 1:1:1, and the button cell is formed in a glove box with the water oxygen content lower than 0.01ppm.
(4) Electrochemical performance detection
The battery was cycled and rate performance tested between 0.1-3V using a blue charge and discharge tester. The result shows that the battery adopting the FeP@CoP/C composite material prepared in the embodiment 2 as the negative electrode has good charge and discharge performance, cycle performance and rate capability.
Example 3
(1) Preparation of ferric oxide micron rod
1.35g of FeCl was weighed out by a balance 3 6H 2 O,1.39g FeSO 4 ·7H 2 O,0.53g of NaCO 3 1mL of concentrated ammonia water is measured by using a cylinder, transferred into a beaker with the volume of 100mL, and then added with 20mL of deionized water, 20mL of glycerol, 20mL of methanol and 10mL of glycol, and magnetically stirred for 10min at the rotating speed of 240 r/min. The mixture was then transferred to a 100mL reactor liner and reacted at 200℃for 6h. Standing the reaction kettle after the reaction is finished, removing upper liquid, centrifugally washing with deionized water for 3 times and ethanol for 2 times at the rotating speed of 7800r/min by using a centrifuge, and then drying in a vacuum drying oven at 80 ℃ for 12 hours to obtain ferric oxide micron rods;
(2) Preparation of iron cobalt phosphide/carbon composite FeP@CoP/C
0.2g of iron oxide micron rods and 0.05g of Co (NO) were weighed out by a balance 3 ) 2 ·6H 2 O,0.05g of CoCl 2 ·6H 2 O,1g CTAB. This was transferred to a beaker having a volume of 100mL, followed by adding 20mL of deionized water, 30mL of methanol, 20mL of glycerol, and after ultrasonic dispersion for 10min, magnetically stirring at 200r/min for 8h. After the reaction is finished, removing upper liquid, centrifugally washing with deionized water for 3 times at the rotating speed of 7800r/min by using a centrifugal machine, and then drying in a vacuum drying oven at 80 ℃ for 12 hours to obtain a product Fe 2 O 3 @Co-MOF; taking 0.2g of product Fe 2 O 3 The @ Co-MOF was placed in the updraft of a corundum ark, 1.8g NaH was taken 2 PO 2 Placing the mixture into the lower air flow of a corundum ark, setting the heating rate to be 3 ℃/min in the argon air flow with the flow rate of 70mL/min, and preserving the heat for 2h when the temperature rises to 300 ℃. And then, setting the heating rate to 5 ℃/min, calcining at a high temperature of 500 ℃ for 2 hours, and slowly cooling to room temperature along with furnace cooling to obtain the iron-cobalt phosphide/carbon composite material FeP@CoP/C.
(3) Preparation of button cell
Assembling the FeP@CoP/C composite material prepared in the step (2) into an electrode, wherein the electrode comprises the following concrete steps: 320mg of active substance FeP@CoP/C composite material, 40mg of conductive agent acetylene black and 40mg of PVDF are uniformly mixed, NMP is used as a solvent and uniformly mixed until the mixed slurry has metallic luster, the prepared electrode slurry is uniformly coated on a copper foil with the thickness of 6cm multiplied by 7cm, and the electrode slurry is taken out after vacuum drying for 12 hours at the temperature of 60 ℃ and punched into a pole piece with the diameter of 8 mm.
The prepared pole piece containing FeP@CoP/C composite material is used as a negative electrode of a battery, a metal lithium sheet is used as a counter electrode and a reference electrode, and an electrolyte is LiPF with the concentration of 1.0mol/L 6 The solvent is ethylene carbonate, dimethyl carbonate and diethyl carbonate according to the weight ratio of 1:1:1, and the button cell is formed in a glove box with the water oxygen content lower than 0.01ppm.
(4) Electrochemical performance detection
And (3) using a blue charge-discharge tester to test the cycle and multiplying power performance of the battery between 0.1 and 3V. The result shows that the battery adopting the FeP@CoP/C composite material prepared in the embodiment 3 as the negative electrode has good charge and discharge performance, cycle performance and rate capability.
Example 4
(1) Preparation of ferric oxide micron rod
4.04g of Fe (NO) was weighed out by a balance 3 ) 2 ·9H 2 O,1.58g of sodium thiosulfate, and 1mL of concentrated ammonia water was measured with a cylinder. This was transferred to a beaker having a volume of 100mL, followed by the addition of 10mL of deionized water, 20mL of glycerol, 20mL of ethanol, and 20mL of DMP. And magnetically stirring for 20min at a rotating speed of 160 r/min. The mixture was then transferred to a 100mL reactor liner and reacted at 220℃for 4h. And after the reaction is finished, standing the reaction kettle, removing upper liquid, centrifugally washing with deionized water for 3 times and ethanol for 2 times at the rotating speed of 7800r/min by using a centrifugal machine, and then drying in a vacuum drying oven at 80 ℃ for 12 hours to obtain the ferric oxide micron rod.
(2) Preparation of iron cobalt phosphide/carbon composite FeP@CoP/C
0.3g of iron oxide micron rods and 0.1g of Co (NO) were weighed out by a balance 3 ) 2 ·6H 2 O,1g of SDBS. This was transferred to a beaker having a volume of 100mL, followed by addition of 20mL of deionized water, 30mL of methanol, 10mL of ethanol, 10mL of ethylene glycol, and after ultrasonic dispersion for 10min, magnetic stirring was performed at a rotational speed of 200r/min for 10h. After the reaction is finished, removing upper liquid, centrifugally washing with deionized water for 3 times at the rotating speed of 7800r/min by using a centrifugal machine, and then drying in a vacuum drying oven at 80 ℃ for 12 hours to obtain a product Fe 2 O 3 @Co-MOF; taking 0.3g of product Fe 2 O 3 Placing @ Co-MOF in the updraft of corundum ark, taking 3g of NaH 2 PO 2 Placing the mixture into the lower air flow of a corundum ark, setting the heating rate to be 3 ℃/min in the argon air flow with the flow rate of 80mL/min, and preserving the heat for 2h when the temperature rises to 300 ℃. And then, setting the heating rate to 5 ℃/min, calcining at a high temperature of 550 ℃ for 3 hours, and slowly cooling to room temperature along with furnace cooling to obtain the iron-cobalt phosphide/carbon composite material FeP@CoP/C.
(3) Preparation of button cell
Assembling the FeP@CoP/C composite material prepared in the step (2) into an electrode, wherein the electrode comprises the following concrete steps: 320mg of active substance FeP@CoP/C composite material, 40mg of conductive agent acetylene black and 40mg of PVDF are uniformly mixed, NMP is used as a solvent and uniformly mixed until the mixed slurry has metallic luster, the prepared electrode slurry is uniformly coated on a copper foil with the thickness of 6cm multiplied by 7cm, and the electrode slurry is taken out after vacuum drying for 12 hours at the temperature of 60 ℃ and punched into a pole piece with the diameter of 8 mm.
The prepared pole piece containing FeP@CoP/C composite material is used as a negative electrode of a battery, a metal lithium sheet is used as a counter electrode and a reference electrode, and an electrolyte is LiPF with the concentration of 1.0mol/L 6 The solvent is ethylene carbonate, dimethyl carbonate and diethyl carbonate according to the weight ratio of 1:1:1, and the button cell is formed in a glove box with the water oxygen content lower than 0.01ppm.
(4) Electrochemical performance detection
The battery was cycled and rate performance tested between 0.1-3V using a blue charge and discharge tester. The battery using the FeP@CoP/C composite material prepared in the embodiment 4 as a negative electrode has good charge and discharge performance, cycle performance and rate capability.
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention.
Claims (14)
1. A method for preparing a layered iron-cobalt phosphide/carbon composite material, which is characterized by comprising the following steps:
(1) Preparation of ferric oxide micron rods: dissolving an iron source and a precipitator in a first reaction medium, stirring, transferring the obtained mixture into a high-pressure reaction kettle liner, and preserving heat for reaction; centrifuging, washing and drying the product after the reaction is finished to obtain an iron oxide micron rod;
(2) Preparation of iron cobalt phosphide/carbon composite material: taking the ferric oxide micron rod obtained in the step (1) as a template, taking cobalt nitrate and/or cobalt chloride as a cobalt source, simultaneously adding a chelating agent, mixing the template, the cobalt source, the chelating agent and a second reaction medium, performing ultrasonic dispersion for 10-12min, stirring, centrifuging, washing and drying the obtained product to obtain the metal cobalt-containing productIron oxide micron bar Fe with machine frame structure 2 O 3 @Co-MOF; in argon flow, fe 2 O 3 Mixing the @ Co-MOF and sodium hydrogen phosphate, and calcining at high temperature to obtain the Fe-Co phosphide/carbon composite material FeP@CoP/C.
2. The method of claim 1, wherein in step (1), the iron source, the precipitant and the first reaction medium are present in a ratio of: 10-13mmol:5-13mmol:70-75mL.
3. The method of claim 2, wherein the iron source is one or more of ferric chloride, ferrous sulfate, ferric nitrate; the precipitant is one or more of oxalic acid, propylene diamine, sodium thiosulfate, sodium bicarbonate, sodium carbonate and ammonia water; the first reaction medium is a deionized water mixed solution containing at least two of glycerol, ethylene glycol, ethanol, methanol and dimethyl phthalate.
4. The process according to claim 2, wherein in step (1), the reaction temperature is 160 to 220 ℃ and the reaction time is 4 to 16 hours.
5. The method according to claim 1, wherein in the step (2), the iron oxide micron rod, the cobalt source, the chelating agent and the second reaction medium are used in an amount ratio of 0.2-0.4g:0.1-0.2g:1-2g:70-75mL.
6. The process according to claim 5, wherein in the step (2), fe 2 O 3 The dosage ratio of the @ Co-MOF to the sodium hydrogen hypophosphite is 0.1-0.3g:1-3g.
7. The method of claim 5, wherein the second reaction medium is a deionized water mixed solution containing at least two of methanol, ethanol, ethylene glycol, and glycerol.
8. The method according to claim 6, wherein the chelating agent is one or more of cetyltrimethylammonium bromide, sodium dodecylbenzenesulfonate, polyvinylpyrrolidone, and 2-methylimidazole.
9. The method according to claim 8, wherein in the step (2), the flow rate of the argon gas flow is 25-80mL/min, and the high-temperature calcination process comprises: the calcination temperature is 300-550 ℃, the temperature rising rate is 2-5 ℃/min, and the time is 2-3h.
10. A button cell, characterized in that the negative electrode of the button cell comprises an iron-cobalt phosphide/carbon composite material obtained by the preparation method according to any one of claims 1-9, and a metallic lithium sheet is used as a counter electrode and a reference electrode.
11. The button cell of claim 10, wherein the negative electrode further comprises a conductive agent acetylene black and a binder polyvinylidene fluoride PVDF; the negative electrode is prepared by the following method: taking N-methyl pyrrolidone NMP as a solvent, and mixing active substances of iron cobalt phosphide/carbon composite material, conductive agent acetylene black and binder polyvinylidene fluoride PVDF according to the dosage ratio of 320-340mg:40-50mg: and (3) uniformly mixing 40-50mg until the mixed slurry has metallic luster, uniformly coating the prepared mixed slurry on the copper foil, vacuum drying at 60-70 ℃ for 12-14h, taking out, and stamping to obtain the pole piece.
12. The button cell of claim 11, wherein the copper foil has dimensions of 6cm x 7cm and the punched pole piece has a diameter of 8-9mm.
13. The coin cell of claim 11 wherein the electrolyte of the coin cell is 1.0mol/L LiPF 6 The solvent is ethylene carbonate, dimethyl carbonate and diethyl carbonate according to the weight ratio of 1:1:1 by volume of the mixture.
14. The coin cell of claim 13 wherein the coin cell is comprised in a glove box having a water oxygen content of less than 0.01ppm.
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| CN107275622A (en) * | 2017-07-11 | 2017-10-20 | 西北大学 | A kind of preparation method and application of graphene@metal phosphides@C nano composites |
| WO2018194263A1 (en) * | 2017-04-19 | 2018-10-25 | 서울대학교산학협력단 | Method for preparing fuel cell catalyst iron phosphide nanoparticles, and iron phosphide nanoparticles prepared thereby |
| CN111569914A (en) * | 2020-04-29 | 2020-08-25 | 国电新能源技术研究院有限公司 | Bimetal phosphide composite material and preparation method and application thereof |
| CN113101955A (en) * | 2021-03-02 | 2021-07-13 | 中国长江三峡集团有限公司 | Preparation method of iron phosphide nano material and application of iron phosphide nano material as electrocatalyst |
| CN113233514A (en) * | 2021-05-14 | 2021-08-10 | 扬州大学 | Preparation method and application of vesicular phosphate radical ion functionalized cobalt oxide nano material |
| CN113782724A (en) * | 2021-09-09 | 2021-12-10 | 安徽工业大学 | Ferro-nickel phosphide-carbon composite material and preparation method and application thereof |
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| CN105895886B (en) * | 2016-06-21 | 2018-09-14 | 中南大学 | A kind of sodium-ion battery transition metal phosphide/porous anode composite and preparation method thereof |
| CN106099106B (en) * | 2016-08-22 | 2019-06-18 | 上海工程技术大学 | It is ultrafast to fill lithium ion battery negative material, preparation method and lithium ion battery |
| CN110176360B (en) * | 2019-04-22 | 2020-09-18 | 山东大学 | Hollow core-shell structure supercapacitor material Fe-Co-S/NF as well as preparation method and application thereof |
| CN112635738B (en) * | 2020-12-22 | 2021-09-21 | 江西理工大学 | Preparation method of FeNiP/C @ MXene composite anode material for lithium ion battery |
| CN113735181B (en) * | 2021-09-06 | 2022-10-11 | 安徽工业大学 | Antimony-cobalt sulfide-carbon composite nanorod and preparation method and application thereof |
| CN113782738A (en) * | 2021-09-09 | 2021-12-10 | 安徽工业大学 | MOF-derived nickel iron phosphide-carbon electrode material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2018194263A1 (en) * | 2017-04-19 | 2018-10-25 | 서울대학교산학협력단 | Method for preparing fuel cell catalyst iron phosphide nanoparticles, and iron phosphide nanoparticles prepared thereby |
| CN107275622A (en) * | 2017-07-11 | 2017-10-20 | 西北大学 | A kind of preparation method and application of graphene@metal phosphides@C nano composites |
| CN111569914A (en) * | 2020-04-29 | 2020-08-25 | 国电新能源技术研究院有限公司 | Bimetal phosphide composite material and preparation method and application thereof |
| CN113101955A (en) * | 2021-03-02 | 2021-07-13 | 中国长江三峡集团有限公司 | Preparation method of iron phosphide nano material and application of iron phosphide nano material as electrocatalyst |
| CN113233514A (en) * | 2021-05-14 | 2021-08-10 | 扬州大学 | Preparation method and application of vesicular phosphate radical ion functionalized cobalt oxide nano material |
| CN113782724A (en) * | 2021-09-09 | 2021-12-10 | 安徽工业大学 | Ferro-nickel phosphide-carbon composite material and preparation method and application thereof |
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Application publication date: 20220325 Assignee: ZHEJIANG CHAOWEI CHUANGYUAN INDUSTRAIAL. Ltd. Assignor: Chaowei Power Group Co.,Ltd. Contract record no.: X2023330000836 Denomination of invention: Preparation Method and Button Battery of a Layered Structure Iron Cobalt Phosphate/Carbon Composite Material Granted publication date: 20230530 License type: Common License Record date: 20231109 |