CN109585804A - A kind of FeSxThe preparation method and application of/C/CNT composite negative pole material - Google Patents
A kind of FeSxThe preparation method and application of/C/CNT composite negative pole material Download PDFInfo
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- CN109585804A CN109585804A CN201811242146.1A CN201811242146A CN109585804A CN 109585804 A CN109585804 A CN 109585804A CN 201811242146 A CN201811242146 A CN 201811242146A CN 109585804 A CN109585804 A CN 109585804A
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- 239000002131 composite material Substances 0.000 title claims abstract description 74
- 239000000463 material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910005432 FeSx Inorganic materials 0.000 claims abstract description 57
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 47
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052742 iron Inorganic materials 0.000 claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 18
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000005864 Sulphur Substances 0.000 claims abstract description 11
- 238000001694 spray drying Methods 0.000 claims abstract description 9
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 8
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 239000008367 deionised water Substances 0.000 claims abstract description 4
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 4
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 7
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 7
- 239000011790 ferrous sulphate Substances 0.000 claims description 7
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical group [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 7
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 7
- -1 Kynoar Chemical compound 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 5
- 229920002472 Starch Polymers 0.000 claims description 4
- 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 4
- 239000008107 starch Substances 0.000 claims description 4
- 235000019698 starch Nutrition 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 239000011295 pitch Substances 0.000 claims description 2
- 229920000128 polypyrrole Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims 1
- 239000004372 Polyvinyl alcohol Substances 0.000 claims 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims 1
- RCHKEJKUUXXBSM-UHFFFAOYSA-N n-benzyl-2-(3-formylindol-1-yl)acetamide Chemical compound C12=CC=CC=C2C(C=O)=CN1CC(=O)NCC1=CC=CC=C1 RCHKEJKUUXXBSM-UHFFFAOYSA-N 0.000 claims 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- 238000005507 spraying Methods 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000004090 dissolution Methods 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract 1
- 239000007773 negative electrode material Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 125000004122 cyclic group Chemical group 0.000 description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229920002239 polyacrylonitrile Polymers 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- JVHAXZCOIRYFSJ-BTVCFUMJSA-N iron;(2r,3s,4r,5r)-2,3,4,5,6-pentahydroxyhexanal Chemical compound [Fe].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O JVHAXZCOIRYFSJ-BTVCFUMJSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a kind of FeSxThe preparation method and application of/C/CNT composite negative pole material, belongs to materials synthesis and field of chemical power source.Source of iron is dissolved into deionized water by the present invention, and carbon source and carbon nanotube is then added and is uniformly mixed, adds sulphur source, spray drying obtains FeS after dissolutionx/ C/CNT composite material precursor；By FeSx/ C/CNT composite material precursor is placed in temperature to calcine 5 ~ 8h under the conditions of 500 ~ 600 DEG C, atmosphere of inert gases, and furnace cooling is adopted and is washed with deionized, and is then dried in vacuo up to FeSx/ C/CNT composite negative pole material.FeS of the inventionx/ C/CNT composite negative pole material can be used for cathode of lithium battery, have high specific capacity and excellent cyclical stability, at room temperature, the charge and discharge cycles under 200 mA/g current densities, by FeSx/ C/CNT composite material calculates, and specific discharge capacity is 630 mAh/g, and coulombic efficiency is up to 99%.
Description
Technical field
The present invention relates to a kind of FeSxThe preparation method and application of/C/CNT composite negative pole material, belongs to materials synthesis and change
Learn field of power supplies.
Background technique
Lithium ion battery is a kind of high-energy density, efficient electrical energy storage device, be widely used in it is small-sized can
Mobile electronic device.As other battery systems, lithium ion battery is mainly by negative electrode material, positive electrode, diaphragm and electrolysis
The big critical material of liquid four is constituted, and the property of material and the performance of lithium ion battery have very important relationship.
Lithium ion battery negative material is that reversibly insertion-deintercalate lithium ions compound, such as lamellar graphite, transition are golden
Belong to sulfide etc..
FeSxAs the negative electrode of lithium ion battery of transient metal sulfide, because of polyelectron electrochemistry involved in charge and discharge process
Reaction, Theoretical Mass specific capacity and Theoretical Mass specific energy are high, but FeSxDuring charge and discharge cycles there are volume expansion,
The problems such as more sulphur intermediates dissolve causes its active material utilization and cycle performance to be deteriorated.
Summary of the invention
For FeS in the prior artxAs transient metal sulfide negative electrode of lithium ion battery there are the problem of, the present invention
A kind of FeS is providedxThe preparation method and application of/C/CNT composite negative pole material, FeS of the inventionx/ C/CNT composite negative pole material
With good conductive network and good sulfur capturing capacity, the utilization rate of active material is improved, assigns the cathode high specific capacity
With excellent cycle performance.
A kind of FeSxThe preparation method of/C/CNT composite negative pole material, the specific steps are as follows:
(1) source of iron is dissolved into deionized water, carbon source and carbon nanotube is then added and be uniformly mixed, add sulphur source, it is molten
Spray drying obtains FeS after solutionx/ C/CNT composite material precursor；
(2) by step (1) FeSxIt is 500 ~ 600 DEG C, atmosphere of inert gases condition that/C/CNT composite material precursor, which is placed in temperature,
5 ~ 8 h of lower calcining, furnace cooling are adopted and are washed with deionized, and are then dried in vacuo up to FeSx/ C/CNT composite negative pole material.
It is Portugal that source of iron, which is ferrous sulfate, ferric sulfate, greening ferrous iron, ferrous nitrate or ferric nitrate, carbon source, in the step (1)
Grape sugar, sucrose, soluble starch, PAN(polyacrylonitrile), PVP(polyvinylpyrrolidone), PEG(polyethylene glycol), the poly- second of PVA(
Enol), PVDF(Kynoar), CMC(sodium carboxymethylcellulose), polypyrrole, phenolic resin or pitch, sulphur source is thio sulphur
Sour sodium.
The molar ratio of step (1) sulphur source and source of iron is (1 ~ 2): 1, the mole mol's of the quality g: source of iron of carbon source
Than for (0.4 ~ 2.0): the ratio of 0.01, the mole mol of the quality g: source of iron of carbon nanotube are (0.25 ~ 1.0): 0.01.
The inlet temperature of step (1) spray drying is 160 ~ 220 DEG C, and outlet temperature is 100 ~ 150 DEG C.
It is a further object of the present invention to provide FeSxFeS prepared by the preparation method of/C/CNT composite negative pole materialx/C/
CNT composite negative pole material.
FeSxApplication of/C/CNT the composite negative pole material in cathode of lithium battery: by FeSx/ C/CNT composite negative pole material is led
Electric agent, binder are uniformly mixed and are coated in metal collector up to cathode of lithium battery, and wherein metal collector is Cu or Cu
Alloy, FeSxFeS in/C/CNT composite negative pole materialxMass percent be 50% ~ 80%.
By cathode of lithium battery of the invention and conventional lithium battery anode, conventional lithium battery diaphragm, conventional lithium battery electrolytes
It is assembled into lithium battery, it is preferred that the electrolyte of lithium battery electrolytes is bis- (trifluoromethyl) sulphonyl imine lithiums, solvent 1,2-
Dimethoxy-ethane and 1, the mixed solvent of 2- dioxolanes, wherein 1,2- dimethoxy-ethane and 1, the volume of 2- dioxolanes
Than being 1 mol/L for the concentration of 1:1, bis- (trifluoromethyl) sulphonyl imine lithiums.
Beneficial effects of the present invention:
(1) FeS of the inventionx/ C/CNT composite negative pole material has good conductive network and good sulfur capturing capacity, improves
The utilization rate of active material assigns the high specific capacity of the cathode and excellent cycle performance；At room temperature, close in 200 mA/g electric currents
Lower charge and discharge cycles are spent, by FeSx/ C/CNT composite material calculates, and specific discharge capacity is 630 mAh/g, and coulombic efficiency is reachable
99%；
(2) FeS of the present inventionx/ C/CNT composite negative pole material has three-dimensional conductive network structure, has height as cathode of lithium battery
Specific capacity, high circulation performance.
Detailed description of the invention
Fig. 1 is FeS in embodiment 1xThe SEM of/C/CNT composite material schemes；
Fig. 2 is FeS in embodiment 1xThe XRD diagram of/C/CNT composite material；
Fig. 3 is FeS in embodiment 1xThe charging and discharging curve figure of/C/CNT composite material；
Fig. 4 is FeS in embodiment 1xThe charge and discharge cycles figure of/C/CNT composite material.
Specific embodiment
Invention is further described in detail With reference to embodiment, but protection scope of the present invention and unlimited
In the content.
A kind of embodiment 1: FeSxThe preparation method of/C/CNT composite negative pole material, the specific steps are as follows:
(1) source of iron (ferrous sulfate) is dissolved into deionized water, carbon source (glucose) and carbon nanotube is then added and mixed
Uniformly, sulphur source (sodium thiosulfate) is added, spray drying obtains FeS after dissolutionx/ C/CNT composite material precursor；Wherein iron
The molar ratio of source (ferrous sulfate) and sulphur source (sodium thiosulfate) is 1:1, and (sulfuric acid is sub- by the quality g: source of iron of carbon source (glucose)
Iron) the ratio of mole mol be 0.8:0.01, the quality g of carbon nanotube: the ratio of the mole mol of source of iron (ferrous sulfate) is
0.4:0.01；The inlet temperature of spray drying is 200 DEG C, and outlet temperature is 130 DEG C；
(2) by step (1) FeSxIt is 500 DEG C, inert gas (argon gas) atmosphere item that/C/CNT composite material precursor, which is placed in temperature,
5 h are calcined under part, furnace cooling is adopted and is washed with deionized, and is then dried in vacuo up to FeSx/ C/CNT composite negative pole material；
The present embodiment FeSxThe SEM of/C/CNT composite material schemes as shown in Figure 1, as can be known from Fig. 1, FeSx/ C/CNT composite material
In micron-sized spherical structure, and FeSxIt is dispersed in the spherical conductive network of C/CNT formation；The C/ of porous structure
CNT spherical conductive network can improve FeSxThe electric conductivity of/C/CNT composite material；FeS can be alleviatedx/ C/CNT composite material is in charge and discharge
Bulk effect in electric cyclic process；The C/CNT spherical frame of porous structure can inhibit the dissolution of polysulfide intermediate, make
FeSx/ C/CNT composite material possesses higher specific capacity and excellent cyclical stability；
The present embodiment FeSxThe XRD diagram of/C/CNT composite material is as shown in Fig. 2, as can be known from Fig. 2, FeSx/ C/CNT composite material
In FeSxFor Fe7S8, it is consistent with standard card JCPDS:01-071-0647；
FeSxApplication of/C/CNT the composite negative pole material in cathode of lithium battery: by FeSx/ C/CNT composite negative pole material, conduction
Agent (acetylene black) mortar grinder is uniformly mixed and obtains negative electrode active material powder, and negative electrode active material powder is added to solvent N-
It is uniformly mixed in N-methyl-2-2-pyrrolidone N and obtains negative electrode active material slurry；Binder (PVDF) is dissolved in Solvents N-methyl-
Binder solution is obtained in 2-Pyrrolidone；Negative electrode active material slurry is uniformly mixed with binder solution and is coated in metal
On collector (copper foil) and it is dried in vacuo cathode of lithium battery to obtain the final product, wherein FeSx/ C/CNT composite negative pole material, conductive agent (acetylene
It is black) it with the mass ratio of binder (PVDF) is 8:1:1；
Electrochemical property test: using the cathode of lithium battery of the present embodiment, lithium metal to electrode, electrolyte 1M LiTFSI-DOL/
DME (v:v=1:1), diaphragm PP/PE/PP assemble button cell in the glove box full of argon gas, and in battery test system
The performance of middle test battery.Charging and discharging currents density is set as 200 mA/g, and charge and discharge blanking voltage is limited to 1.0 ~ 3.0 V；
The present embodiment FeSxThe charging and discharging curve figure of/C/CNT composite material as shown in figure 3, as can be seen from Figure 3, discharge platform is 1.7 V,
Discharge platform is almost unchanged in cyclic process；The present embodiment FeSxCharge and discharge cycles figure such as Fig. 4 institute of/C/CNT composite material
Show, as can be seen from Figure 4, FeSx/ C/CNT composite material charge and discharge cycles under 200 mA/g current densities, by FeSx/ C/CNT is compound
Material calculates, and specific discharge capacity is maintained at 630 mAh/g, coulombic efficiency 99.2%.
Embodiment 2: the present embodiment FeSxThe preparation method and embodiment 1FeS of/C/CNT composite negative pole materialx/ C/CNT is multiple
The preparation method for closing negative electrode material is almost the same, the difference is that, carbon source is sodium carboxymethylcellulose, and (carboxymethyl is fine for carbon source
Tie up plain sodium) quality g: the ratio of the mole mol of source of iron (ferrous sulfate) be 0.8:0.01；The inlet temperature of spray drying is
220 DEG C, outlet temperature is 150 DEG C；
The present embodiment electrochemical property test method is same as Example 1, from the present embodiment FeSx/ C/CNT composite material fills
For discharge curve it is found that discharge platform is 1.7 V, discharge platform is almost unchanged in cyclic process；From the present embodiment FeSx/C/
The charge and discharge cycles figure of CNT composite material；FeSx/ C/CNT composite material charge and discharge cycles under 200 mA/g current densities, are pressed
FeSx/ C/CNT composite material calculates, and specific discharge capacity is maintained at 640 mAh/g, coulombic efficiency 99.3%.
Embodiment 3: the present embodiment FeSxThe preparation method and embodiment 1FeS of/C/CNT composite negative pole materialx/ C/CNT is multiple
The preparation method for closing negative electrode material is almost the same, the difference is that, carbon source is soluble starch, carbon source (soluble starch)
Quality g: the ratio of the mole mol of source of iron (ferrous sulfate) is 0.6:0.01；The inlet temperature of spray drying is 180 DEG C, outlet
Temperature is 120 DEG C；
The present embodiment electrochemical property test method is same as Example 1, from the present embodiment FeSx/ C/CNT composite material fills
For discharge curve it is found that discharge platform is 1.7 V, discharge platform is almost unchanged in cyclic process；From the present embodiment FeSx/C/
The charge and discharge cycles figure of CNT composite material；FeSx/ C/CNT composite material charge and discharge cycles under 200 mA/g current densities, are pressed
FeSx/ C/CNT composite material calculates, and specific discharge capacity is maintained at 610 mAh/g, coulombic efficiency 99.1%.
Embodiment 4: the present embodiment FeSxThe preparation method and embodiment 1FeS of/C/CNT composite negative pole materialx/ C/CNT is multiple
The preparation method for closing negative electrode material is almost the same, the difference is that, source of iron is frerrous chloride, and carbon source is polyacrylonitrile, carbon source
The quality g of (polyacrylonitrile): the ratio of the mole mol of source of iron (frerrous chloride) is 1.2:0.01；The quality g: iron of carbon nanotube
The ratio of the mole mol in source (frerrous chloride) is 0.6:0.01；The inlet temperature of spray drying is 160 DEG C, outlet temperature 100
℃；
The present embodiment electrochemical property test method is same as Example 1, from the present embodiment FeSx/ C/CNT composite material fills
For discharge curve it is found that discharge platform is 1.7 V, discharge platform is almost unchanged in cyclic process；From the present embodiment FeSx/C/
The charge and discharge cycles figure of CNT composite material；FeSx/ C/CNT composite material charge and discharge cycles under 200 mA/g current densities, are pressed
FeSx/ C/CNT composite material calculates, and specific discharge capacity is maintained at 620 mAh/g, coulombic efficiency 99.2%.
Embodiment 5: the present embodiment FeSxThe preparation method and embodiment 1FeS of/C/CNT composite negative pole materialx/ C/CNT is multiple
The preparation method for closing negative electrode material is almost the same, the difference is that, source of iron is ferrous nitrate, and carbon source is phenolic resin, carbon source
The quality g of (phenolic resin): the ratio of the mole mol of source of iron (ferrous nitrate) is 0.5:0.01；The quality g: iron of carbon nanotube
The ratio of the mole mol in source (ferrous nitrate) is 0.5:0.01；
The present embodiment electrochemical property test method is same as Example 1, from the present embodiment FeSx/ C/CNT composite material fills
For discharge curve it is found that discharge platform is 1.7 V, discharge platform is almost unchanged in cyclic process；From the present embodiment FeSx/C/
The charge and discharge cycles figure of CNT composite material；FeSx/ C/CNT composite material charge and discharge cycles under 200 mA/g current densities, are pressed
FeSx/ C/CNT composite material calculates, and specific discharge capacity is maintained at 620 mAh/g, coulombic efficiency 99.3%.
Claims (6)
1. a kind of FeSxThe preparation method of/C/CNT composite negative pole material, which is characterized in that specific step is as follows:
(1) source of iron is dissolved into deionized water, carbon source and carbon nanotube is then added and be uniformly mixed, add sulphur source, it is molten
Spray drying obtains FeS after solutionx/ C/CNT composite material precursor；
(2) by step (1) FeSxIt is 500 ~ 600 DEG C, under the conditions of atmosphere of inert gases that/C/CNT composite material precursor, which is placed in temperature,
5 ~ 8 h are calcined, furnace cooling is adopted and is washed with deionized, and is then dried in vacuo up to FeSx/ C/CNT composite negative pole material.
2. FeS according to claim 1xThe preparation method of/C/CNT composite negative pole material, it is characterised in that: iron in step (1)
Source is ferrous sulfate, ferric sulfate, greening ferrous iron, ferrous nitrate or ferric nitrate, and carbon source is glucose, sucrose, soluble starch, gathers
Acrylonitrile, polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol, Kynoar, sodium carboxymethylcellulose, polypyrrole, phenolic aldehyde
Resin or pitch, sulphur source are sodium thiosulfate.
3. FeS according to claim 1xThe preparation method of/C/CNT composite negative pole material, it is characterised in that: step (1) sulphur source
Molar ratio with source of iron is (1 ~ 2): the ratio of 1, the mole mol of the quality g: source of iron of carbon source are (0.4 ~ 2.0): 0.01, carbon is received
The ratio of the mole mol of the quality g: source of iron of mitron is (0.25 ~ 1.0): 0.01.
4. FeS according to claim 1xThe preparation method of/C/CNT composite negative pole material, it is characterised in that: step (1) is spraying
Dry inlet temperature is 160 ~ 220 DEG C, and outlet temperature is 100 ~ 150 DEG C.
5. any one of claim 1 ~ 4 FeSxFeS prepared by the preparation method of/C/CNT composite negative pole materialx/C/CNT
Composite negative pole material.
6. the FeS of claim 5xApplication of/C/CNT the composite negative pole material in cathode of lithium battery.
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| CN113511710A (en) * | 2021-05-27 | 2021-10-19 | 安徽中科索纳新材料科技有限公司 | Electrode active material for capacitance adsorption of lead ions and preparation method and application thereof |
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Application publication date: 20190405 |