CN114122386A - Tin phosphide @ carbon composite negative electrode active precursor material, negative electrode active material, negative electrode and preparation of negative electrode - Google Patents
Tin phosphide @ carbon composite negative electrode active precursor material, negative electrode active material, negative electrode and preparation of negative electrode Download PDFInfo
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- CN114122386A CN114122386A CN202010893569.0A CN202010893569A CN114122386A CN 114122386 A CN114122386 A CN 114122386A CN 202010893569 A CN202010893569 A CN 202010893569A CN 114122386 A CN114122386 A CN 114122386A
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- Prior art keywords
- lithium
- carbon
- negative electrode
- simple substance
- sulfur battery
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- 239000000463 material Substances 0.000 title claims abstract description 77
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 75
- 239000002243 precursor Substances 0.000 title claims abstract description 64
- 239000002131 composite material Substances 0.000 title claims abstract description 57
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 131
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 96
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000000126 substance Substances 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000002905 metal composite material Substances 0.000 claims abstract description 10
- 239000002105 nanoparticle Substances 0.000 claims abstract description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 88
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 47
- 239000002245 particle Substances 0.000 claims description 37
- 229910052751 metal Inorganic materials 0.000 claims description 34
- 239000002184 metal Substances 0.000 claims description 34
- 239000002041 carbon nanotube Substances 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 229910052698 phosphorus Inorganic materials 0.000 claims description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 13
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 13
- 239000011574 phosphorus Substances 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 230000001939 inductive effect Effects 0.000 claims description 12
- 239000007790 solid phase Substances 0.000 claims description 12
- 239000011230 binding agent Substances 0.000 claims description 11
- 239000002134 carbon nanofiber Substances 0.000 claims description 11
- 238000004729 solvothermal method Methods 0.000 claims description 11
- 238000011049 filling Methods 0.000 claims description 10
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 9
- 238000011068 loading method Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 238000004070 electrodeposition Methods 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000006182 cathode active material Substances 0.000 claims description 4
- 238000006138 lithiation reaction Methods 0.000 claims description 4
- 239000006258 conductive agent Substances 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 2
- 229910008365 Li-Sn Inorganic materials 0.000 claims description 2
- 229910006759 Li—Sn Inorganic materials 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 2
- 238000013329 compounding Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 125000005341 metaphosphate group Chemical group 0.000 claims description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 235000011150 stannous chloride Nutrition 0.000 claims description 2
- 239000001119 stannous chloride Substances 0.000 claims description 2
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 claims description 2
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims 1
- 229910001416 lithium ion Inorganic materials 0.000 claims 1
- 230000008021 deposition Effects 0.000 abstract description 25
- 230000008569 process Effects 0.000 abstract description 6
- 239000010406 cathode material Substances 0.000 abstract description 3
- 238000004090 dissolution Methods 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 238000000151 deposition Methods 0.000 description 24
- 238000012360 testing method Methods 0.000 description 20
- 238000009826 distribution Methods 0.000 description 13
- 238000002156 mixing Methods 0.000 description 11
- 239000000758 substrate Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 238000011160 research Methods 0.000 description 9
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 7
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Inorganic materials [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 7
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 7
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 6
- 239000011889 copper foil Substances 0.000 description 6
- 230000001351 cycling effect Effects 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 210000001787 dendrite Anatomy 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000006230 acetylene black Substances 0.000 description 5
- 239000011149 active material Substances 0.000 description 5
- 210000004027 cell Anatomy 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000006911 nucleation Effects 0.000 description 4
- 238000010899 nucleation Methods 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 2
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000006183 anode active material Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 239000011163 secondary particle Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- IHCCLXNEEPMSIO-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 IHCCLXNEEPMSIO-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- 229910020879 Sn-Li Inorganic materials 0.000 description 1
- 229910008888 Sn—Li Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
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- 230000000877 morphologic effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000007581 slurry coating method Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002195 synergetic effect 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
- H01M4/58—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/08—Other phosphides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
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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
- H01M4/62—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
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- Crystallography & Structural Chemistry (AREA)
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- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the field of lithium metal battery cathode materials. The tin phosphide @ carbon composite cathode active precursor material comprises a carbon simple substance framework and tin phosphide nanoparticles which are embedded on the outer surface of the carbon simple substance framework and are distributed in a dot shape. The invention also discloses the application of the lithium-philic negative active material in the preparation of a lithium metal composite electrode. According to the material, the tin phosphide nano-dots are uniformly dispersed and distributed on the outer surface of the simple substance carbon skeleton, and based on the innovative morphology and structural characteristics, the rich specific surface and good conductivity of the simple substance carbon skeleton are combined, so that the local current density is effectively reduced, uniform deposition and dissolution of lithium metal in the continuous circulation process are realized, the growth of dendritic crystals is effectively avoided, and the cycle life of the lithium sulfur battery is greatly prolonged.
Description
Technical Field
The invention belongs to the technical field of lithium metal batteries, and particularly relates to the field of lithium-sulfur battery lithium metal composite active materials.
Background
The lithium-sulfur battery is a new generation energy storage system which is constructed by a simple substance sulfur positive electrode and a lithium metal negative electrode and has high theoretical energy density and quick charging characteristic. The lithium metal has extremely high theoretical specific capacity of 3860mAh g-1And the lowest electrochemical potential-3.04V (relative to a standard hydrogen electrode), have been considered the most desirable negative electrode material for lithium batteries. However, lithium metal without host structure is prone to large volume effects during repeated deposition/dissolution processes, resulting in a greatly reduced cycle life; on the other hand, the inherent unevenness of the lithium metal surface causes uneven lithium deposition, which in turn causes uncontrollable lithium dendrites, causes short circuit and even fire explosion of the battery,further industrial application of the lithium metal negative electrode is hindered.
At present, the volume effect in the lithium metal circulation process is eliminated mainly by constructing a 3D porous skeleton structure, including graphene, hollow carbon spheres, carbon fibers, glass fibers, foam metal skeletons and the like, wherein the carbon material becomes an important host material for inhibiting the volume change of lithium metal due to the advantages of light weight, good conductivity, strong toughness and the like, for example, Chongwu Zhou and the like [ Zhang a, Fang X, Shen C, et al. Compared with pure lithium metal, the high specific surface area can effectively reduce local current density; however, at high current densities, lithium metal deposition is not uniform, resulting in uncontrolled lithium dendrites, reduced coulombic efficiency, and reduced cycle life.
Aiming at the problem of uneven deposition of lithium metal in a three-dimensional space, researchers mainly modify the surface of a carbon skeleton at present. Lysine, et al [ Hong B, Fan H, Cheng X B, et al, spatial university of lithium metal in 3D Janus hosts [ J].Energy Storage Materials,2019,16: 259-266.]Through carrying out the metal spraying treatment on the lower surface of the carbon paper, the lithium is guided to be uniformly deposited in the three-dimensional structure, and the coulomb efficiency and the circulation stability are effectively improved. Hulian et al [ Zhang Y, Liu B, Hitz E, et al.A carbon-based 3D current collector with surface protection for Li metal anode [ J].Nano Research,2017,10:1356-1365.]Surface modification of carbon nanotubes by chemical vapor deposition to obtain Al2O3The carbon nanotube sponge is modified to have high specific surface area and stable Al2O3The performance of the lithium negative electrode is greatly improved at the layer interface.
Although the current research has made great progress, the lithium cathode needs to be further researched to maintain uniform deposition of lithium, lower volume effect and reduce internal polarization of the lithium cathode under high current density.
The invention content is as follows:
the invention provides a tin phosphide @ carbon composite cathode active precursor material (also called precursor material for short) of a lithium-sulfur battery, aiming at solving the problems of uneven deposition and uncontrollable growth of lithium dendrite in the circulation process of the existing lithium-sulfur battery metal lithium cathode material, and providing a lithium-sulfur battery metal lithium cathode active precursor material which can induce lithium to be uniformly nucleated and deposited, improve the problem of uneven lithium deposition under high current, reduce the volume effect and internal polarization of the lithium cathode and improve the circulation performance of the lithium-sulfur battery metal lithium cathode.
The second object of the present invention is to provide a method for preparing the precursor material.
The third objective of the present invention is to provide an application of the precursor material.
A fourth object of the present invention is to provide a lithium metal composite anode active material (also referred to as a lithium metal composite active material or simply as an active material) for a lithium sulfur battery.
A fifth object of the present invention is to provide a method for preparing the composite anode active material using the precursor material.
A sixth object of the present invention is to provide a negative electrode for a lithium-sulfur battery. Aims to obtain a lithium cathode without dendrites and under a high current density (3-8 mA-cm)-2) Has good cycle performance.
The seventh object of the invention is to provide a method for preparing the negative electrode of the lithium-sulfur battery based on the precursor material.
An eighth object of the present invention is to provide a lithium-sulfur battery equipped with the negative electrode.
A tin phosphide @ carbon composite cathode active precursor material for a lithium-sulfur battery comprises a carbon simple substance framework and tin phosphide nanoparticles which are embedded on the outer surface of the carbon simple substance framework and distributed in a punctate manner (uniformly dispersed and distributed);
the carbon simple substance framework is a one-dimensional carbon simple substance and/or a zero-dimensional carbon simple substance.
The invention belongs to the technical field of lithium-sulfur battery metal lithium cathode materials, and aims to solve the problems that the lithium-sulfur battery metal lithium cathode is not uniformly deposited, has a large volume effect and is not ideal in electrochemical performance. In order to solve the technical problem, the research of the invention discovers that the deposition uniformity and the structural stability of the lithium-sulfur battery metal lithium cathode in the circulating process can be effectively improved based on the innovative morphology and structural characteristics by innovatively adopting the one-dimensional simple carbon substance and/or the zero-dimensional simple carbon substance as the substrate and uniformly dispersing and distributing the tin phosphide nano-dots on the outer surface of the substrate, and the electrochemical performance of the lithium-sulfur battery, particularly the circulating stability under large current, can be unexpectedly improved.
In the invention, the structural characteristics of the one-dimensional carbon simple substance and/or zero-dimensional carbon simple substance substrate and the dispersion distribution characteristics of the tin phosphide nano particles on the outer surface of the substrate of the precursor material are the keys for realizing the good capacity, coulombic efficiency and cycle stability of the precursor material in a lithium-sulfur battery.
The carbon simple substance skeleton is at least one of a carbon nano tube, a carbon nano fiber, a carbon hollow sphere and a carbon solid sphere; the carbon simple substance skeleton is graphitized carbon and/or amorphous carbon.
Preferably, the simple substance carbon skeleton is a carbon nanotube.
More preferably, the diameter of the carbon nano tube is 5-100 nm; further preferably 10 to 40 nm;
preferably, the thickness of the tube wall of the carbon nano tube is 1-20 nm; more preferably 4 to 8 nm.
In the invention, the dispersion distribution mode of the tin phosphide particles and the distribution form of the outer surface of the substrate are the key points for realizing good electrochemical performance of the tin phosphide in the lithium-sulfur battery. Research shows that for the lithium-sulfur battery lithium metal composite negative electrode, the uniform and punctiform tin phosphide particles can effectively reduce nucleation overpotential of lithium deposition and improve uniform deposition of lithium metal. Further research finds that the long-acting cycling stability of the lithium-sulfur battery lithium metal battery is further improved by controlling the particle size and distribution amount of the tin phosphide particles.
Preferably, the particle size of the tin phosphide particles is 0.1-10 nm; further preferably 3 to 6 nm;
preferably, in the precursor material, the content of the tin phosphide particles is 5 wt% to 50 wt%; more preferably 10 to 30 wt%.
The invention also provides a preparation method of the tin phosphide @ carbon composite cathode active precursor material for the lithium-sulfur battery, which comprises the steps of carrying out solvothermal reaction on a raw material solution containing a Sn (II) source, a simple substance carbon skeleton and alcohol to form a punctiform Sn oxide on the surface of the simple substance carbon skeleton; then carrying out solid-phase phosphating treatment on the phosphorus source and a phosphorus source in an inert atmosphere to obtain the phosphorus-containing material;
in the raw material solution, the molar concentration of the Sn (II) source (calculated by Sn (II) ions) is 0.2-1 mol/L;
the concentration of the carbon simple substance skeleton is 15-40 g/L.
The research of the invention discovers that the one-dimensional and zero-dimensional carbon simple substance is innovatively adopted as the substrate, the combination control of the concentration of a divalent Sn (II) source), the concentration of a solvent in the solvothermal stage and the concentration of the Sn (II) source and the concentration of the carbon simple substance skeleton in the solvothermal reaction starting solution is matched, the formation of the Sn oxide distributed in a dotted manner on the surface of the carbon simple substance skeleton in an ectopic mode is facilitated, the solid-phase phosphating treatment is further matched, and the Sn oxide distributed in the dotted manner can be converted into the Sn phosphide in situ to obtain the precursor material with the morphology.
In the preparation method, how to successfully construct the punctiform Sn oxide in the solvothermal process is the key for ensuring the good effect of the prepared material in the aspect of being used as the lithium-sulfur battery metal lithium composite negative electrode. Therefore, the invention innovatively researches and discovers that the ectopic deposition outer surface is provided by adopting one-dimensional and zero-dimensional carbon simple substance, and the Sn oxide material in the punctiform distribution form can be successfully constructed based on the combined control of the solvothermal process system, the Sn (II) source and the carbon simple substance concentration. On the basis of the Sn oxide material, the Sn oxide can be converted into phosphide in situ by further matching with solid-phase phosphating treatment, and the punctiform distribution form is successfully reserved.
Preferably, the sn (ii) source is at least one of stannous chloride and stannous sulfate.
Preferably, the alcohol is at least one of ethanol, methanol and 2-propanol.
In the present invention, controlling the molar concentration of the sn (ii) source helps to successfully build the material in a dotted distribution that has a good impact in lithium sulfur batteries. The concentration is not controlled in the required range, the material distributed in a point shape is difficult to obtain, and the electrochemical improvement of the lithium-sulfur battery is not facilitated.
Preferably, the molar concentration of the Sn (II) source in the raw material solution is 0.6-0.8 mol/L.
Similarly, on the basis of controlling the molar concentration of the Sn (II) source, the concentration of the carbon simple substance skeleton is further controlled in a coordinated manner, which is favorable for obtaining the precursor material with good application effect in the lithium-sulfur battery.
Preferably, the molar concentration of the carbon single substance skeleton in the raw material solution is 20-40 g/L.
The research of the invention also finds that under the solvothermal system, the distribution form and the structure of Sn in the carbon substrate can be further controlled by further matching with the solvothermal temperature control. Preferably, the temperature of the solvothermal is 100-250 ℃, and preferably 140-190 ℃; more preferably 150 to 160 ℃. Research shows that under the preferable solvothermal system and solvothermal temperature, the punctate distribution form of the Sn oxide can be effectively controlled, and the performance of the Sn oxide as a lithium metal negative electrode precursor material of the lithium-sulfur battery can be further improved.
Preferably, the solvothermal time is 5-15 hours, preferably 8-12 hours;
in the invention, on the basis of the solvothermal property, the solid-phase phosphating means is further matched, so that the synergy can be realized, Sn oxide distributed in a dot shape is converted into phosphide in an original state, and the dot distribution state is maintained and improved, thereby being beneficial to the synergistic improvement of the performance of the Sn oxide in the negative electrode of the lithium-sulfur battery.
Preferably, the phosphorus source is at least one of metaphosphate and hypophosphite.
Preferably, the amount of the phosphorus source is not less than the theoretical molar amount of completely reacting Sn, and preferably 1 to 4 times the theoretical molar amount.
Preferably, the mass ratio of the phosphorus source to the tin dioxide @ carbon composite active precursor material is 1: 1-6: 1.
The solid phase phosphating treatment of the formula is characterized in that SnO is embedded on the surface in a punctiform manner2Mixing the carbon composite material of the particles with a phosphorus source material, heating the mixture in an inert atmosphere, and reacting the phosphorus source material to generate PH3By means of pH3SnO2Reduction of the particles to Sn4P3Particles and original SnO is maintained2The structure and the point distribution characteristics of the particles obtain the precursor material.
Preferably, the temperature of the solid-phase phosphating treatment is 250-500 ℃, and more preferably 250-300 ℃.
Preferably, the temperature rise rate in the solid-phase phosphating process is 1-2 ℃/min, and more preferably 1-1.5 ℃/min.
Preferably, the time for the solid-phase phosphating is 10min to 3 hours, preferably 10min to 1 hour.
The invention also discloses an application of the tin phosphide @ carbon composite cathode active precursor material of the lithium-sulfur battery, and the lithium-carrying treatment (lithiation-induced lithium carrying) is carried out on the precursor material to prepare the metal lithium composite cathode active material of the lithium-sulfur battery.
The application can adopt the existing method to fill lithium into the precursor material, so that the precursor material reacts with the lithium and carries out induced lithium loading, and the lithium-sulfur battery metal lithium composite negative electrode material is obtained.
The invention also provides a lithium-sulfur battery lithium metal composite cathode active material (also called lithium metal composite active material) which comprises the carbon simple substance framework, an inducing layer compounded on the outer surface of the carbon simple substance framework and a lithium metal simple substance compounded on the surface of the inducing layer; the inducing layer comprises Li-Sn alloy and Li3P。
The metal lithium composite active material of the invention has Sn uniformly distributed in a punctiform way at the initial stage of the lithiation process4P3The particles react with lithium to form a lithium-containing compound3An inducing layer of P and Sn-Li alloy, the inducing layerThe conductive layer can effectively reduce the lithium nucleation overpotential, so that lithium metal is promoted to be uniformly deposited on the inducing layer, and a compact lithium simple substance deposition layer is obtained.
The lithium-sulfur battery lithium metal composite negative electrode active material is obtained by lithiating and then carrying out lithium loading on a lithium-sulfur battery tin phosphide @ carbon composite negative electrode active precursor material.
The invention also provides a lithium-sulfur battery cathode which comprises the lithium-sulfur battery metal lithium composite cathode active material.
Preferably, the lithium-sulfur battery negative electrode comprises a negative electrode current collector and a metal lithium active layer compounded on the surface of the current collector; the metal lithium active layer comprises conductive carbon, the lithium-sulfur battery metal lithium composite negative electrode active material and a binder for binding and compounding the material on the surface of a current collector.
Preferably, the metal lithium is compounded on the surface of the inducing layer, and also filled in the gaps between the metal lithium composite negative active material particles of the lithium sulfur battery.
The invention also provides a preparation method of the lithium-sulfur battery cathode, the precursor material, the conductive agent and the binder are slurried and compounded on the surface of the cathode current collector, and the cathode precursor is obtained after solidification and drying; and then carrying out lithium loading (lithium filling) treatment on the negative electrode precursor, so that the precursor material is lithiated in advance, and lithium metal is induced to be deposited on the surface of the lithiation induction layer and in the gap of the precursor material, thereby preparing the negative electrode of the lithium-sulfur battery.
In the invention, the precursor material can be sprayed to obtain secondary particles of the precursor material, and then the secondary particles are subjected to slurry coating with a conductive agent and a binder and loaded with lithium to obtain the negative electrode.
In the invention, the lithium loading treatment method is melting lithium filling or electrodeposition lithium filling; further preferred is electrodeposition lithium filling.
The current collector may be any current collector known in the art, such as a planar metal current collector, a copper foil, or the like.
The binder may be a binding polymer well known in the industry, such as PVDF.
The lithium carrying amount in the negative electrode of the lithium-sulfur battery can be adjusted according to needs, and the preferable lithium carrying amount is 1-20 mA/cm2。
The invention also provides an application of the cathode of the lithium-sulfur battery, and the cathode is used as the cathode of the lithium-sulfur battery.
The invention also provides a lithium-sulfur battery comprising the cathode.
Has the advantages that:
1. the invention provides a tin phosphide @ carbon composite cathode active precursor material for a lithium-sulfur battery, and the material with the morphology has unexpected technical effects in the aspect of a lithium metal cathode of the lithium-sulfur battery.
According to the precursor material, the one-dimensional and zero-dimensional carbon simple substance is used as a substrate, and tin phosphide is uniformly dispersed and distributed on the surface of the substrate. In addition, the precursor material can greatly increase the specific surface area and reduce the apparent current density; the abundant and evenly distributed tin phosphide particles provide lithium-philic sites which can preferentially induce nucleation of lithium metal, so that the lithium metal can be evenly deposited in the porous carbon skeleton cavity, and the volume effect is slowed down.
2. The material can effectively induce lithium metal to uniformly react and deposit in the lithium metal battery, can obviously reduce nucleation potential, reduce polarization, and obviously improve the electrochemical performance of the lithium metal battery, particularly the cycling stability.
Moreover, the composite lithium metal cathode made of the precursor material can realize high coulombic efficiency, long cycle life and high energy density under high current density. In addition, the one-dimensional and zero-dimensional carbon frameworks have excellent conductivity, and meanwhile, the abundant specific surface can well relieve the uneven lithium deposition under the high current density, so that good electrochemical conditions are created for realizing the stable deposition/dissolution of lithium metal.
3. In order to obtain the composite material with the morphological characteristics and the composite negative electrode, the invention also provides a preparation process for phosphorization of the carbon skeleton and Sn (II) under the solvothermal-inert atmosphere, and innovatively discovers that the material with the special morphology and excellent electrochemical performance in a lithium metal battery can be obtained by cooperatively controlling parameters such as a solvothermal system, the concentrations of Sn (II) and a carbon substrate in solvothermal, the temperature of solvothermal and the like and further matching with the solid-phase phosphorization means.
Detailed Description
The following is a detailed description of the preferred embodiments of the invention and is not intended to limit the invention in any way, i.e., the invention is not intended to be limited to the embodiments described below, and modifications and alternative compounds that are conventional in the art are intended to be included within the scope of the invention as defined in the claims.
In the following cases, the heating rate in the heating process is 1-1.5 ℃/min unless otherwise stated.
Example 1
The outer diameter of the Carbon Nano Tube (CNT) is 40nm, and the thickness of the tube wall is 7 nm. First 4.51g SnCl2·2H2O (0.02moL) was dissolved in 25mL of ethanol (0.8moL/L), and 1.00g of carbon nanotubes was added to completely immerse the solution. After magnetic stirring for 60 minutes, the suspension obtained is transferred to an autoclave and heated to 150 ℃ for a solvothermal reaction for 10 hours. Then washing the obtained product with deionized water and drying to obtain SnO2@ CNT composites. SnO2Mixing the @ CNT composite material (1.4g) with 6g of sodium hypophosphite, uniformly mixing, placing in a tubular furnace, introducing argon, heating to 280 ℃, preserving heat for 30min, naturally cooling, washing with deionized water, and drying to obtain Sn4P3@ CNT composites.
Sn is added4P3@ CNT composite anode precursor material (Sn prepared)4P3@ CNT composite) is mixed with PVDF and acetylene black which are binding agents according to the mass ratio of 8:1:1, NMP is added to the mixture to be slurried and then is uniformly coated on a copper foil, the mixture is dried to be used as a working electrode, a metal lithium sheet is used as a counter electrode, and 1M LiTFSI/DOL: DME (volume ratio is 1:1) contains 1 wt.% LiNO3Button cell (half cell) assembly, lithium deposition test and charge-discharge cycling test were performed for the electrolyte. Meanwhile, the carbon nanotube is used for manufacturing an electrode as a comparison sample to carry out corresponding deposition test and charge-discharge cycle test.
The experimental result shows that compared with pure carbon nano-tubes with smooth surfaces, the granular Sn4P3Sn particles are uniformly dispersed on the outer surface of the carbon nano tube in a point-like manner4P3The average particle diameter of the particles is about 5nm, Sn4P3The content was 30 wt.%. In the subsequent lithium deposition experiment, the metallic lithium can be uniformly nucleated and deposited on Sn4P3The @ CNT composite surface avoids uneven lithium deposition and the appearance of lithium dendrites.
At 3mA/cm2At current density of Sn4P3The @ CNT material composite electrode has a cycle life of 3 times or more that of a pure carbon nanotube (carbon nanotube before being composited) at the same coulombic efficiency.
Example 2
Compared with the embodiment 1, the difference is that the carbon nano-fiber is used for replacing the carbon nano-tube, specifically:
carbon Nanofibers (CNF), 100nm in diameter. First 4.51g SnCl2·2H2O (0.02moL) was dissolved in 25mL of ethanol, and 1.00g of carbon nanofibers were added to completely immerse the solution. After magnetic stirring for 60 minutes, the suspension obtained is transferred to an autoclave and heated to 150 ℃ for a solvothermal reaction for 10 hours. Then washing the obtained product with deionized water and drying to obtain SnO2@ CNF composite. SnO2Mixing the @ CNF composite material (1.4g) with 6g of sodium hypophosphite, uniformly mixing, placing in a tubular furnace, introducing argon, heating to 280 ℃, preserving heat for 30min, naturally cooling, washing with deionized water, and drying to obtain Sn4P3@ CNF composite.
Sn is added4P3Mixing the @ CNF composite anode precursor material with binders PVDF and acetylene black according to the mass ratio of 8:1:1, adding NMP, slurrying, uniformly coating on a copper foil, drying, using a metal lithium sheet as a counter electrode, and using 1M LiTFSI/DOL: DME (volume ratio of 1:1) containing 1 wt.% LiNO3Button cell assembly, lithium deposition testing and charge-discharge cycling testing were performed for the electrolyte. Meanwhile, the carbon nanofiber electrode is used as a comparison sample to carry out corresponding deposition test and charge-discharge cycle test.
The experimental result shows that compared with pure carbon nano fiber, the granular Sn4P3Particles are uniformly dispersed and distributed on the surface of the carbon nano fiber in a punctiform manner, and Sn4P3The average particle diameter of the particles is about 5nm, Sn4P3The content was 20 wt.%. In the subsequent lithium deposition experiment, the metallic lithium can be uniformly nucleated and deposited on Sn4P3The surface of the @ CNF composite and the interstices formed thereof avoid uneven lithium deposition and the occurrence of lithium dendrites.
At 3mA/cm2At current density of Sn4P3The cycle life of the @ CNF material composite electrode under the same coulombic efficiency is more than 2 times of that of the pure carbon nanofiber (CNF before treatment).
Example 3
Compared with the embodiment 1, the difference is mainly that the concentration of Sn is 1M, specifically:
the outer diameter of the Carbon Nano Tube (CNT) is 40nm, and the thickness of the tube wall is 7 nm. Firstly, 5.64g of SnCl2·2H2O (0.025moL) was dissolved in 25mL of ethanol (1moL/L), and 1.00g of carbon nanotubes was added to completely immerse the carbon nanotubes in the solution. After magnetic stirring for 60 minutes, the suspension obtained is transferred to an autoclave and heated to 150 ℃ for a solvothermal reaction for 10 hours. Then washing the obtained product with deionized water and drying to obtain SnO2@ CNT composites. SnO2Mixing 1.4g of @ CNT composite material with 6g of sodium hypophosphite, uniformly mixing, placing in a tubular furnace, introducing argon, heating to 280 ℃, preserving heat for 30min, naturally cooling, washing with deionized water, and drying to obtain Sn4P3@ CNT composites.
SnCl2·2H2Sn on the surface of the carbon nano tube when the O ethanol solution is 1mol/L4P3The particles are not uniformly distributed and part of the particles are stacked and agglomerated.
Example 3-1
Compared with example 3, the difference is only that in the solvothermal starting solution, the concentration of Sn is 0.2M, and Sn is prepared4P3@ CNT is compounded with a negative electrode active precursor material.
Examples 3 to 2
Compared with example 3, the difference is only that in the solvothermal starting solution, the concentration of Sn is 0.5M, and Sn is prepared4P3@ CNT is compounded with a negative electrode active precursor material.
Examples 3 to 3
Compared with example 3, the difference is only that in the solvothermal starting solution, the concentration of Sn is 0.6M, and Sn is prepared4P3@ CNT is compounded with a negative electrode active precursor material.
As is clear from examples 1, 3-1, 3-2 and 3-3, 0.2mol/L of SnCl was obtained2·2H2Obvious Sn is difficult to see on the surface of the carbon nano tube treated by the O ethanol solution4P3Particles, SnCl2·2H2After the molar concentration of O reaches 0.5mol/L, Sn4P3The particles are less and are unevenly distributed, and a part of the surface has larger blanks. Sn is more uniformly embedded on the surface of the carbon nano tube at 0.5-0.8mol/L4P3Nanoparticles of Sn4P3The particle size of the nano particles is about 5 nm. And SnCl2·2H2After the molar concentration of O is increased to 1mol/L, Sn4P3Uneven particle distribution and increased particle diameter, Sn4P3The particles are partially stacked and agglomerated. Thus, SnCl2·2H2The concentration of O in the ethanol solution is preferably 0.6-0.8 mol/L.
The half-cell was assembled as in example 1 and the electrochemical measurements were carried out:
sn prepared in example 1, example 3-1 and example 3-24P3Mixing the @ CNT composite material with PVDF (polyvinylidene fluoride) and acetylene black serving as binders in a mass ratio of 8:1:1, adding NMP (N-methyl pyrrolidone) to form slurry, uniformly coating the slurry on a copper foil, drying the slurry to form a working electrode, using a lithium metal sheet as a counter electrode, and using 1M LiTFSI/DOL (volume ratio of 1:1) containing 1 wt.% LiNO3Button cell assembly, lithium deposition testing and charge-discharge cycling testing were performed for the electrolyte. At 3mA/cm2The current density of the current sensor was selected for charge-discharge cycle testing, and the test results are shown in table 1 below:
TABLE 1
The result shows that the electrochemical performance of the electrode of the tin phosphide @ carbon composite negative electrode active material obtained when the concentration of the Sn (II) source in the solvothermal reaction is 0.8M is optimal.
Example 4
Compared with example 1, the difference is mainly that the temperature of solvothermal is 120 ℃ to produce Sn4P3@ CNT is compounded with a negative electrode active precursor material.
Example 4-1
Compared with example 4, the difference is only that the solvothermal temperature is 140 ℃ to produce Sn4P3@ CNT is compounded with a negative electrode active precursor material.
Example 4 to 2
Compared with example 4, the difference is only that the solvothermal temperature is 160 ℃ to produce Sn4P3@ CNT is compounded with a negative electrode active precursor material.
Examples 4 to 3
Compared with example 4, the difference is only that the solvothermal temperature is 180 ℃ to produce Sn4P3@ CNT is compounded with a negative electrode active precursor material.
Examples 4 to 4
Compared with example 4, the difference is only that the solvothermal temperature is 200 ℃ to produce Sn4P3@ CNT is compounded with a negative electrode active precursor material.
The examples 1, 4-1, 4-2 were carried outExamples 4-3 and 4-4 show that Sn is present on the surface of the carbon nanotube at a solvothermal temperature of 120 ℃4P3The number of particles is less; sn on the surface of the carbon nano tube when the temperature is raised to 140 ℃, 150 ℃, 160 ℃ and 180 DEG C4P3The quantity of the particles is improved and the particles are uniformly distributed, thereby being beneficial to forming the special appearance. And Sn is generated when the solvothermal temperature is 200 DEG C4P3The increase in particle size and the decrease in the number of particles are detrimental to Sn4P3A homogeneous distribution of the particles. Therefore, the solvent thermal reaction temperature is 100-250 ℃, and is preferably 140-180 ℃, which is beneficial to forming the punctiform and uniformly distributed Sn on the surface of the carbon skeleton4P3Particles.
And (3) electrochemical performance testing:
the electrochemical measurements were carried out as in example 1, specifically:
sn prepared in example 1, example 4-1, example 4-2, example 4-3 and example 4-44P3Mixing the @ CNT composite material with PVDF (polyvinylidene fluoride) and acetylene black serving as binders in a mass ratio of 8:1:1, adding NMP (N-methyl pyrrolidone) to form slurry, uniformly coating the slurry on a copper foil, drying the slurry to form a working electrode, using a lithium metal sheet as a counter electrode, and using 1M LiTFSI/DOL (volume ratio of 1:1) containing 1 wt.% LiNO3Button cell assembly, lithium deposition testing and charge-discharge cycling testing were performed for the electrolyte. At 3mA/cm2The current density of (A) was selected for the charge-discharge cycle test, and the test results are shown in Table 2 below:
TABLE 2
The result shows that the electrochemical performance of the obtained tin phosphide @ carbon composite negative electrode active material is optimal when the reaction temperature in the solvothermal reaction is 150-160 ℃.
Example 5
The electrical performance of the lithium-sulfur battery (full battery) is determined, and specifically comprises the following steps:
sn prepared in example 14P3Mixing the @ CNT composite negative electrode precursor material with binders PVDF and acetylene black according to the mass ratio of 8:1:1, adding NMP, slurrying, uniformly coating on a copper foil, drying, using a metal lithium sheet as a counter electrode, and using 1M LiTFSI/DOL: DME (volume ratio of 1:1) containing 1 wt.% LiNO3As an electrolyte, at a current density of 0.5mA/cm2Bottom deposition of 5mAh/cm2And obtaining the metal lithium composite negative electrode. Then the lithium sulfur battery is formed with a mesoporous carbon positive electrode rich in S simple substance, and 1M LiTFSI/DOL DME (volume ratio is 1:1) contains 1 wt.% LiNO3In the electrolyte of (1), a charge-discharge cycle test was performed at 1C.
Example 6:
the electrical performance of the lithium-sulfur battery (full battery) is determined, and specifically comprises the following steps:
compared with example 5, the difference is only that Sn4P3The method for lithium loading (lithium filling) treatment of the @ CNT composite negative electrode precursor is melting lithium filling, that is: and contacting the grade sheet containing the cathode precursor material with molten metal lithium at 250 ℃ in an oxygen-free dry environment to obtain the metal lithium composite cathode. Then the lithium sulfur battery is formed with a mesoporous carbon positive electrode rich in S simple substance, and 1M LiTFSI/DOL DME (volume ratio is 1:1) contains 1 wt.% LiNO3In the electrolyte of (1), a charge-discharge cycle test was performed at 1C.
The results of the experimental tests are shown in table 3:
TABLE 3
The results show that Sn is obtained by filling lithium by electrodeposition4P3The @ CNT composite lithium metal negative electrode has optimal electrochemical performance.
Claims (10)
1. A tin phosphide @ carbon composite cathode active precursor material for a lithium-sulfur battery is characterized in that: comprises a carbon simple substance framework and tin phosphide nano-particles which are embedded on the outer surface of the carbon simple substance framework and are distributed in a point shape;
the carbon simple substance framework is a one-dimensional carbon simple substance and/or a zero-dimensional carbon simple substance.
2. The tin phosphide @ carbon composite anode active precursor material of claim 1, wherein: the carbon simple substance skeleton is at least one of a carbon nano tube, a carbon nano fiber, a carbon hollow sphere and a carbon solid sphere; the carbon simple substance skeleton is graphitized carbon and/or amorphous carbon;
preferably, the carbon simple substance skeleton is a carbon nanotube;
more preferably, the diameter of the carbon nano tube is 5-100 nm; further preferably 10 to 40 nm;
preferably, the thickness of the tube wall of the carbon nano tube is 1-20 nm; more preferably 4 to 8 nm.
3. The tin phosphide @ carbon composite anode active precursor material of claim 1, wherein: the particle size of the tin phosphide nano-particles is 0.1-10 nm; further preferably 3 to 6 nm;
preferably, in the tin phosphide @ carbon composite anode active precursor material, the content of tin phosphide nanoparticles is 5 wt% -50 wt%; more preferably 10 to 30 wt%.
4. The preparation method of the tin phosphide @ carbon composite negative electrode active precursor material for the lithium-sulfur battery as defined in any one of claims 1 to 3, is characterized by comprising the following steps: carrying out solvothermal reaction on a raw material solution containing a Sn (II) source, a carbon simple substance skeleton and alcohol to form a Sn oxide distributed in a dotted manner on the surface of the carbon simple substance skeleton; then carrying out solid-phase phosphating treatment on the phosphorus source and a phosphorus source in an inert atmosphere to obtain the phosphorus-containing material;
in the raw material solution, the molar concentration of the Sn (II) source is 0.2-1 mol/L;
the concentration of the carbon simple substance skeleton is 15-40 g/L.
5. The method of claim 4, wherein: the Sn (II) source is at least one of stannous chloride and stannous sulfate;
preferably, the alcohol is at least one of ethanol, methanol and 2-propanol
Preferably, the concentration of the carbon simple substance skeleton is 20-40 g/L;
preferably, the temperature of the solvothermal reaction is 100-250 ℃, preferably 140-190 ℃;
preferably, the solvothermal time is 5-15 hours, preferably 8-12 hours;
preferably, the phosphorus source is at least one of metaphosphate and hypophosphite;
the using amount of the phosphorus source is not less than the theoretical molar amount of completely reacting Sn, and is preferably 1-4 times of the theoretical molar amount;
the temperature of the solid-phase phosphating treatment is 250-500 ℃; the heating rate is 1-2 ℃/min;
preferably, the time of the solid-phase phosphating treatment is 10min to 3h, preferably 10min to 1 h.
6. The application of the tin phosphide @ carbon composite anode active precursor material for the lithium-sulfur battery as defined in any one of claims 1 to 3 or the tin phosphide @ carbon composite anode active precursor material for the lithium-sulfur battery prepared by the preparation method as defined in claim 4 or 5 is characterized in that: and carrying out lithium loading treatment on the lithium-containing composite material to obtain the lithium-sulfur battery lithium metal composite negative electrode active material.
7. The lithium-sulfur battery metal lithium composite cathode active material is characterized by comprising a carbon simple substance framework, an inducing layer compounded on the outer surface of the carbon simple substance framework and a metal lithium simple substance compounded on the surface of the inducing layer; the inducing layer comprises Li-Sn alloy and Li3P；
Preferably, the lithium-sulfur battery metal lithium composite negative electrode active material is obtained by loading lithium on the lithium-sulfur battery tin phosphide @ carbon composite negative electrode active precursor material described in any one of claims 1 to 3 or the lithium-sulfur battery tin phosphide @ carbon composite negative electrode active precursor material prepared by the preparation method described in claim 4 or 5.
8. A lithium sulfur battery negative electrode comprising the lithium sulfur battery lithium metal composite negative electrode active material according to claim 7;
preferably, the lithium ion battery comprises a negative electrode current collector and a metal lithium active layer compounded on the surface of the current collector; the metal lithium active layer comprises conductive carbon, the lithium-sulfur battery metal lithium composite negative electrode active material and a binder for binding and compounding the material on the surface of a current collector;
preferably, the metal lithium is compounded on the surface of the inducing layer, and also filled in the gaps between the metal lithium composite negative active material particles of the lithium sulfur battery.
9. A preparation method of a lithium-sulfur battery cathode is characterized in that the precursor material of any one of claims 1 to 3 or the precursor material prepared by the preparation method of any one of claims 4 to 5, a conductive agent and a binder are slurried and compounded on the surface of a cathode current collector, and a cathode precursor is obtained after curing and drying; then carrying out lithium loading treatment on the negative electrode precursor to ensure that the precursor material is lithiated in advance and induce lithium metal to deposit on the surface of the lithiation inducing layer and in the gap of the precursor material, thus preparing the negative electrode of the lithium-sulfur battery;
preferably, the lithium loading treatment method is melting lithium filling or electrodeposition lithium filling; further preferred is electrodeposition lithium filling.
10. A lithium-sulfur battery comprising the negative electrode according to claim 8 or the negative electrode produced by the production method according to claim 9.
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| CN113488650A (en) * | 2020-08-28 | 2021-10-08 | 中南大学 | Cu3P @ P-doped mesoporous carbon composite framework and preparation method and application thereof |
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