CN110571500A - lithium-sulfur semi-flow battery - Google Patents
lithium-sulfur semi-flow battery Download PDFInfo
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- CN110571500A CN110571500A CN201910880904.0A CN201910880904A CN110571500A CN 110571500 A CN110571500 A CN 110571500A CN 201910880904 A CN201910880904 A CN 201910880904A CN 110571500 A CN110571500 A CN 110571500A
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- lithium
- sulfur
- flow battery
- negative electrode
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- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 150
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 226
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 125
- 239000005077 polysulfide Substances 0.000 claims abstract description 105
- 229920001021 polysulfide Polymers 0.000 claims abstract description 102
- 150000008117 polysulfides Polymers 0.000 claims abstract description 102
- 239000007788 liquid Substances 0.000 claims abstract description 100
- 239000003792 electrolyte Substances 0.000 claims abstract description 92
- 239000002131 composite material Substances 0.000 claims abstract description 66
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000011230 binding agent Substances 0.000 claims abstract description 54
- 239000006258 conductive agent Substances 0.000 claims abstract description 54
- 239000011149 active material Substances 0.000 claims abstract description 45
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 39
- 239000011593 sulfur Substances 0.000 claims abstract description 39
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 5
- 239000000956 alloy Substances 0.000 claims abstract description 5
- 239000006185 dispersion Substances 0.000 claims description 58
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 56
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 43
- 239000011812 mixed powder Substances 0.000 claims description 36
- 238000002360 preparation method Methods 0.000 claims description 35
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 30
- 229910052799 carbon Inorganic materials 0.000 claims description 29
- 238000009210 therapy by ultrasound Methods 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000005711 Benzoic acid Substances 0.000 claims description 15
- 235000010233 benzoic acid Nutrition 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 10
- 239000010935 stainless steel Substances 0.000 claims description 10
- 229910001220 stainless steel Inorganic materials 0.000 claims description 10
- 229910021389 graphene Inorganic materials 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000004108 freeze drying Methods 0.000 claims description 8
- 238000007710 freezing Methods 0.000 claims description 8
- 230000008014 freezing Effects 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 6
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 6
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 6
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 6
- 229940078494 nickel acetate Drugs 0.000 claims description 6
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 claims description 6
- 239000006230 acetylene black Substances 0.000 claims description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 5
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910000881 Cu alloy Inorganic materials 0.000 claims description 3
- 229910000676 Si alloy Inorganic materials 0.000 claims description 3
- 229910001128 Sn alloy Inorganic materials 0.000 claims description 3
- ZVLDJSZFKQJMKD-UHFFFAOYSA-N [Li].[Si] Chemical compound [Li].[Si] ZVLDJSZFKQJMKD-UHFFFAOYSA-N 0.000 claims description 3
- CTUFHBVSYAEMLM-UHFFFAOYSA-N acetic acid;platinum Chemical compound [Pt].CC(O)=O.CC(O)=O CTUFHBVSYAEMLM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- OPHUWKNKFYBPDR-UHFFFAOYSA-N copper lithium Chemical compound [Li].[Cu] OPHUWKNKFYBPDR-UHFFFAOYSA-N 0.000 claims description 3
- 239000011888 foil Substances 0.000 claims description 3
- UIDWHMKSOZZDAV-UHFFFAOYSA-N lithium tin Chemical compound [Li].[Sn] UIDWHMKSOZZDAV-UHFFFAOYSA-N 0.000 claims description 3
- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 claims 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 238000004146 energy storage Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 46
- 239000002033 PVDF binder Substances 0.000 description 38
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 38
- 238000002156 mixing Methods 0.000 description 24
- 239000011248 coating agent Substances 0.000 description 19
- 238000000576 coating method Methods 0.000 description 19
- 238000012360 testing method Methods 0.000 description 18
- 238000000227 grinding Methods 0.000 description 10
- 239000011268 mixed slurry Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 10
- 239000012300 argon atmosphere Substances 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- VEJOYRPGKZZTJW-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;platinum Chemical compound [Pt].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O VEJOYRPGKZZTJW-FDGPNNRMSA-N 0.000 description 8
- 239000013543 active substance Substances 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 239000000463 material Substances 0.000 description 5
- DRZUOPCJWAJOAG-UHFFFAOYSA-N CC(=O)C.CC(=O)C.[Ni] Chemical compound CC(=O)C.CC(=O)C.[Ni] DRZUOPCJWAJOAG-UHFFFAOYSA-N 0.000 description 4
- DMUNQEXYOBRAQK-UHFFFAOYSA-N [Pt].CC(=O)C.CC(=O)C Chemical compound [Pt].CC(=O)C.CC(=O)C DMUNQEXYOBRAQK-UHFFFAOYSA-N 0.000 description 4
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 4
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Chemical compound CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 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 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical group [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 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
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
-
- 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
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
the invention discloses a lithium-sulfur semi-flow battery, which comprises a sulfur flow positive electrode area, a lithium metal negative electrode area and a diaphragm; the liquid sulfur positive region comprises a working electrode and lithium polysulfide catholyte; the working electrode comprises an active material, a conductive agent, a binder and a current collector; the active material is Ni/C composite material, Pt/C composite material or Pt3a Ni/C composite material; the lithium polysulfide cathode electrolyte consists of lithium polysulfide dissolved in lithium sulfur electrolyte; the lithium metal negative electrode region comprises a lithium metal negative electrode and a lithium sulfur electrolyte, and the lithium metal negative electrode is lithium metal or lithium metal alloy; the diaphragm is a single ion film; the lithium-sulfur semi-flow battery has high energy density, high power density and long service life, and can be widely used as a power supply of various machines such as an electric vehicle or a hybrid electric vehicle and also as a large-scale energy storage device of a power grid.
Description
Technical Field
The invention relates to the field of electrochemical energy, in particular to a lithium-sulfur semi-flow battery with high energy density, high power density and long cycle life.
Background
In recent decades, the use of solar energy, tidal energy, and wind energy has increased, and electric vehicles with low carbon dioxide emissions have been spreading. Therefore, in order to effectively utilize renewable energy, the development of high-performance, safe, inexpensive, and environmentally friendly energy conversion and storage systems is imperative. Preferred among these energy storage systems are lithium ion batteries and supercapacitors. Lithium ion batteries are common electrochemical devices for storing electrical energy. However, despite their commercial success, lithium ion batteries have failed to meet the high power demands required for applications such as power tools, electric vehicles, and efficient storage of renewable energy. In contrast, supercapacitors, in addition to providing higher energy densities than conventional dielectric capacitors, also show promise for high power systems because they can instantaneously provide higher power densities than batteries. However, the energy density of supercapacitors is still insufficient for new applications requiring high energy and high power density.
to overcome these disadvantages, research on lithium ion batteries has focused on electrode material improvements, for example, the use of silicon negative electrodes and lithium rich positive electrodes. However, these materials themselves suffer from several drawbacks, including low first-pass coulombic efficiency, unsatisfactory rate performance, poor cycle life, poor thermal characteristics, and significant voltage decay. In fact, alternative battery systems, such as lithium air batteries, lithium sulfur batteries, and sodium/magnesium ion batteries, have proven to be superior to lithium ion batteries in terms of energy/power density, safety, and cost. However, these systems also have their own drawbacks. For example, in the process of charging and discharging the lithium-sulfur battery, the utilization rate of active substances of the battery is reduced and the cycle life of the battery is shortened due to the dissolution and shuttling of intermediates of the lithium-sulfur battery; meanwhile, the rate performance of the battery is poor due to poor conductivity of active substances, namely sulfur and lithium sulfide, and in order to improve the conductivity, a large amount of conductive additives are required to be added, so that the content of the active substances is reduced, the volume energy density of the battery is low, and the high energy density of the lithium-sulfur battery is difficult to exert. Therefore, in order to solve these problems, a new class of lithium-sulfur flow battery systems has recently been proposed. The system includes the use of a working electrode having electrocatalytic activity, a lithium polysulfide catholyte, a separator, and a negative region including a lithium metal negative electrode and a conventional lithium sulfur electrolyte. Although the lithium-sulfur semi-flow battery has high energy density and power density, the problems of catalytic activity and stability of the working electrode and selectivity of the separator must be solved to realize commercial application thereof.
disclosure of Invention
the invention provides a lithium-sulfur semi-flow battery with high energy density, high power density and long service life, which comprises a sulfur flow positive electrode area, a lithium metal negative electrode area and a diaphragm.
The liquid sulfur positive region includes a working electrode, a lithium polysulfide catholyte.
the working electrode comprises an active material capable of catalyzing the conversion of lithium polysulfide, a conductive agent, a binder and a current collector; the mass ratio of the active material capable of catalyzing the conversion of lithium polysulfide to the conductive agent to the binder is 8:1: 1; the conductive agent and the binder are common products of commercial batteries, preferably Super p is used as the conductive agent, and preferably polyvinylidene fluoride (PVDF) is used as the binder; the current collector is one of common current collectors such as aluminum foil, stainless steel mesh and carbon paper or is self-supporting, and the stainless steel mesh is preferred.
The active material capable of catalyzing the conversion of lithium polysulfide is Ni/C composite material, Pt/C composite material and Pt3Ni, Pt-loaded Ni/C composite material or the like3A conductive carrier of Ni.
The lithium polysulfide cathode electrolyte is formed by dissolving lithium polysulfide in lithium sulfur electrolyte, and the concentration of the lithium polysulfide is 0.1-2 mol/L, preferably 1 mol/L; the solvent of the lithium-sulfur electrolyte is R (CH)2CH2o) n-R 'wherein n =1-6, R and R' are methyl or ethyl, the solute is lithium difluorooxalato borate, lithium bistrifluoromethylsulfonylimide, lithium difluorosulfonylimide, lithium difluorophosphate or lithium hexafluorophosphate, and the concentration of the lithium sulfur electrolyte is 1 mol/L.
The lithium metal negative electrode region comprises a lithium metal negative electrode and lithium sulfur electrolyte, the lithium metal negative electrode is lithium metal or lithium metal alloy, and the lithium metal alloy is lithium tin alloy, lithium silicon alloy or lithium copper alloy; the solvent of the lithium-sulfur electrolyte is R (CH)2CH2O) n-R 'wherein n =1-6, R and R' are methyl or ethyl, the solute is lithium difluorooxalato borate, lithium bistrifluoromethylsulfonylimide, lithium difluorosulfonylimide, lithium difluorophosphate or lithium hexafluorophosphate, and the concentration of the lithium sulfur electrolyte is1mol/L。
the diaphragm comprises one of a single ion film such as PP or PE and three-layer films such as PP/PE/PP.
the preparation method of the Ni/C composite material comprises the following specific steps:
(1) carrying out ultrasonic treatment on a C conductive carrier and deionized water for 1 ~ 5 hours to obtain a carbon ~ based carrier dispersion liquid with the concentration of 1 ~ 10mg/mL, wherein the C conductive carrier is one of graphene, Super p, carbon black, acetylene black, CNT and the like;
(2) adding nickel acetate or nickel nitrate into the carbon ~ based carrier dispersion liquid obtained in the step (1) according to the mass ratio of C to Ni of 5 ~ 15:1, and performing ultrasonic treatment for 1 ~ 5 hours to obtain a mixed dispersion liquid;
(3) Rapidly freezing the mixed dispersion liquid in the step (2) by using liquid nitrogen, and freeze-drying by using a freeze dryer to obtain mixed powder;
(4) and (3) under the protection of Ar gas, placing the mixed powder in the step (3) in a tube furnace, heating to 700 ~ 900 ℃ at a heating rate of 5 ℃/min, calcining for 1 ~ 3 hours, and naturally cooling to obtain the Ni/C composite material.
The preparation method of the Pt/C composite material is the same as that of the Ni/C composite material, and nickel acetate or nickel nitrate in the step (2) is replaced by platinum acetate or platinum nitrate.
The Pt3the preparation method of the Ni/C composite material comprises the following specific steps:
(1) adding a C conductive carrier into a round ~ bottom flask containing DMF, and carrying out ultrasonic treatment for 1 ~ 5 hours to obtain a carbon ~ based carrier dispersion liquid with the concentration of 1 ~ 10mg/mL, wherein the C conductive carrier is one of graphene, Super p, carbon black, acetylene black, CNT and the like;
(2) Mixing platinum diacetone (Pt (acac)2) Nickel diacetone (Ni (acac)2) Push button Pt (acac)2:Ni(acac)2adding C into the carbon ~ based carrier dispersion liquid obtained in the step (1) at a mass ratio of 8:8:20 ~ 24:8:60, adding benzoic acid, adding the benzoic acid according to a mass ratio of diacetone platinum to benzoic acid of 8:50 ~ 70, and performing ultrasonic treatment for 1 ~ 5 hours to obtain a mixed dispersion liquid;
(3) heating the mixed dispersion liquid in the step (2) in a constant ~ temperature water bath at the temperature of 150 ~ 170 ℃, and reacting for 20 ~ 24 hours;
(4) Centrifugally separating the product obtained in the step (3) to obtain Pt3A Ni/C composite material.
the preparation method of the working electrode comprises the following specific steps:
(1) mixing 80 parts by weight of an active material capable of catalyzing the conversion of lithium polysulfide and 10 parts by weight of a conductive agent and grinding to obtain mixed powder;
(2) and (2) stirring and mixing the mixed powder obtained in the step (1) and 10 parts by weight of binder solution, coating the mixed slurry on a current collector until the thickness of the current collector is preferably 10 ~ 500 microns, and performing vacuum drying at 60 ℃ for 10 ~ 24 hours to remove the solvent to obtain the working electrode.
the lithium-sulfur semi-flow battery is assembled by taking a working electrode and a lithium polysulfide catholyte as a liquid sulfur positive electrode region, taking a lithium metal negative electrode and a lithium sulfur electrolyte as a lithium metal negative electrode region and a diaphragm together according to the assembly mode of a commercial liquid flow battery, so that the lithium-sulfur semi-flow battery is obtained; electrochemical redox of lithium polysulfide occurs in the liquid flow sulfur positive electrode area, lithium stripping/deposition occurs in the lithium metal negative electrode area, lithium polysulfide cathode electrolyte in the liquid flow sulfur positive electrode area also plays a role in providing active substance lithium polysulfide, electrolyte between the working electrode and the counter electrode mainly plays a role in transferring charges by conducting lithium ions, meanwhile, solute lithium salt has good solubility and ionic conductivity in the electrolyte, which has important influence on the working temperature, specific energy, cycle efficiency, safety performance and the like of the battery, the middle diaphragm separates the positive electrode active substance and the negative electrode active substance of the battery, only allows lithium ions to pass through, prevents any electron current between the positive electrode and the negative electrode from directly passing through, and avoids short circuit of the battery; the ion flow has as low a resistance as possible when passing through it, and it has a high energy density and power density.
The invention has the beneficial effects that:
1. The lithium-sulfur semiliquid flow battery has the performances of high energy density, high power density and long service life, can be used as a secondary battery for a driving power supply in mobile information instruments such as mobile phones and notebook computers, and can be widely used as a power supply of various machines such as electric vehicles or hybrid electric vehicles.
2. The lithium-sulfur semi-flow battery shows strong energy and power density and excellent cycle performance, the lithium-sulfur semi-flow battery utilizes the working electrode to catalyze the mutual conversion among lithium polysulfides, and meanwhile, the conversion among the lithium polysulfides is liquid-liquid reaction, so that the utilization rate and the reaction rate of active substances are improved, and the sulfur active substances have high theoretical specific capacity (such as sulfur: 1675 mAh/g), therefore, the lithium-sulfur semi-flow battery can overcome the challenges brought by the traditional lithium-sulfur battery, and finally realizes high capacity, good rate characteristic and excellent cycle performance, thereby being used as an advanced energy storage device.
3. The method has low implementation cost and large-scale application potential.
drawings
FIG. 1 is a schematic diagram of the structure of a lithium-sulfur semi-flow battery of example 1;
FIG. 2 shows Pt in example 93SEM image of Ni/C composite material;
FIG. 3 shows Pt in example 93A charge-discharge curve diagram of a lithium-sulfur semi-flow battery with a Ni/C composite material as a working electrode;
FIG. 4 shows Pt in example 93And (3) a cycle performance diagram of the lithium-sulfur semi-flow battery with the Ni/C composite material as the working electrode.
Detailed Description
The invention will be further illustrated by the following examples in conjunction with the drawings, but it will be understood that the examples are for the purpose of illustrating embodiments of the invention and that the scope of protection is not limited by the examples described without departing from the scope of the subject matter of the invention.
Additional objects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. In the following description, "%" is not particularly specified on a mass basis.
example 1
High energythe lithium-sulfur semi-flow battery with high density, high power density and long service life comprises a sulfur flow positive electrode area, a lithium metal negative electrode area and a diaphragm; the liquid sulfur positive region comprises a working electrode and lithium polysulfide catholyte; the working electrode comprises an active material capable of catalyzing the conversion of lithium polysulfide, a conductive agent, a binder and a current collector; the mass ratio of the active material capable of catalyzing the conversion of lithium polysulfide to the conductive agent to the binder is 8:1: 1; the conductive agent and the binder are common products of commercial batteries, preferably Super p is used as the conductive agent, and preferably polyvinylidene fluoride (PVDF) is used as the binder; the current collector is a stainless steel mesh; the active material capable of catalyzing the conversion of lithium polysulfide is a Ni/C composite material; the lithium polysulfide cathode electrolyte is formed by dissolving lithium polysulfide in lithium sulfur electrolyte, and the concentration of the lithium polysulfide is 1 mol/L; the lithium metal negative electrode region comprises a lithium metal negative electrode and a lithium sulfur electrolyte, the lithium metal negative electrode is lithium metal, and the diaphragm is a three-layer porous membrane made of PP/PE/PP materials; the solvent of the lithium-sulfur electrolyte of the embodiment is represented by the formula R (CH)2CH2O) n-R 'wherein n =1, R and R' are both methyl, the solute is lithium difluorooxalato borate, and the concentration of the lithium sulfur electrolyte is 1 mol/L.
The preparation process of the lithium-sulfur semi-flow battery of the embodiment specifically comprises the following steps:
A. the preparation method of the Ni/C composite material comprises the following specific steps:
(1) Adding the C conductive carrier graphene dispersion liquid (3 wt%) into a beaker filled with deionized water, and carrying out ultrasonic treatment for 1 hour to obtain a carbon-based carrier dispersion liquid with the concentration of 1 mg/mL;
(2) Adding nickel nitrate into the carbon-based carrier dispersion liquid obtained in the step (1) according to the mass ratio of C to Ni of 5:1, and performing ultrasonic treatment for 5 hours to obtain a mixed dispersion liquid;
(3) rapidly freezing the mixed dispersion liquid in the step (2) by using liquid nitrogen, and freeze-drying by using a freeze dryer to obtain mixed powder;
(4) Placing the mixed powder in the step (3) in a tube furnace under the protection of Ar gas, heating to 800 ℃ at the speed of 5 ℃/min, calcining for 2 hours, and naturally cooling to obtain a Ni/C composite material;
B. The preparation method of the working electrode comprises the following specific steps:
(1) mixing and grinding 80 parts by weight of the active material Ni/C composite material capable of catalyzing the conversion of lithium polysulfide prepared in the step A and 10 parts by weight of conductive agent Super p to obtain mixed powder;
(2) stirring and mixing the mixed powder obtained in the step (1) and 10 parts by weight of a binder polyvinylidene fluoride (PVDF), and coating the mixed slurry on a current collector; coating the slurry until the thickness of the current collector is 10 microns, and performing vacuum drying at 60 ℃ for 24 hours to remove the solvent to obtain a working electrode;
C. And (2) preparing the lithium-sulfur semi-flow battery, as shown in figure 1, assembling the working positive electrode obtained in the step (B) and the lithium polysulfide catholyte which are used as a liquid sulfur positive electrode area together, assembling a lithium metal negative electrode and the lithium sulfur electrolyte which are used as a lithium metal negative electrode area together with a diaphragm according to the assembly mode of the commercial flow battery, and superposing the working electrode, the catholyte, the PP/PE/PP three-layer porous membrane, the lithium sulfur electrolyte and the lithium metal negative electrode in sequence in a glove box in an argon atmosphere to obtain the lithium-sulfur semi-flow battery.
and testing the performance of the battery in a battery test system, wherein the charge ~ discharge cut ~ off voltage is 1.8V ~ 2.6V, and the charge ~ discharge current density is 0.50 mA/cm.
Example 2
a lithium-sulfur semi-flow battery with high energy density, high power density and long service life comprises a sulfur flow positive electrode area, a lithium metal negative electrode area and a diaphragm; the liquid sulfur positive region comprises a working electrode and lithium polysulfide catholyte; the working electrode comprises an active material capable of catalyzing the conversion of lithium polysulfide, a conductive agent, a binder and a current collector; the mass ratio of the active material capable of catalyzing the conversion of lithium polysulfide to the conductive agent to the binder is 8:1: 1; the conductive agent and the binder are common products of commercial batteries, preferably Super p is used as the conductive agent, and preferably polyvinylidene fluoride (PVDF) is used as the binder; the current collector is an aluminum foil; the active material capable of catalyzing the conversion of lithium polysulfide is a Pt/C composite material; the lithium polysulfide cathode electrolyte is formed by dissolving lithium polysulfide in lithium sulfur electrolyte, and the concentration of the lithium polysulfide is 1 mol/L; the lithium metal negative electrode region comprises a lithium metal negative electrode and a lithium sulfur electrolyte, the lithium metal negative electrode is lithium metal,The diaphragm is a three-layer porous membrane made of PP/PE/PP materials; the solvent of the lithium-sulfur electrolyte of the embodiment is represented by the formula R (CH)2CH2o) n-R 'wherein n =2, R and R' are both ethyl, the solute is lithium bistrifluoromethylsulfonimide, and the concentration of the lithium sulfur electrolyte is 1 mol/L.
The preparation process of the lithium-sulfur semi-flow battery of the embodiment specifically comprises the following steps:
A. the preparation method of the Ni/C composite material comprises the following specific steps:
(1) Adding the C conductive carrier graphene dispersion liquid (3 wt%) into a beaker filled with deionized water, and carrying out ultrasonic treatment for 2 hours to obtain a carbon-based carrier dispersion liquid with the concentration of 5 mg/mL;
(2) Adding nickel acetate into the carbon-based carrier dispersion liquid in the step (1) according to the mass ratio of C to Ni of 10:1, and performing ultrasonic treatment for 3 hours to obtain a mixed dispersion liquid;
(3) rapidly freezing the mixed dispersion liquid in the step (2) by using liquid nitrogen, and freeze-drying by using a freeze dryer to obtain mixed powder;
(4) Placing the mixed powder in the step (3) in a tube furnace under the protection of Ar gas, heating to 700 ℃ at a speed of 5 ℃/min, calcining for 3 hours, and naturally cooling to obtain a Ni/C composite material;
B. The preparation method of the working electrode comprises the following specific steps:
(1) Mixing and grinding 80 parts by weight of the active material Ni/C composite material capable of catalyzing the conversion of lithium polysulfide prepared in the step A and 10 parts by weight of conductive agent Super p to obtain mixed powder;
(2) stirring and mixing the mixed powder obtained in the step (1) and 10 parts by weight of a binder polyvinylidene fluoride (PVDF), and coating the mixed slurry on a current collector; coating the slurry until the thickness of the current collector is 30 microns, and performing vacuum drying at 60 ℃ for 24 hours to remove the solvent to obtain a working electrode;
C. and C, preparing the lithium-sulfur semi-flow battery, namely using the working anode obtained in the step B and the lithium polysulfide catholyte together as a liquid sulfur anode region, using the lithium metal cathode and the lithium sulfur electrolyte as a lithium metal cathode region, assembling the lithium metal cathode and the lithium sulfur electrolyte together with a diaphragm into the battery according to the assembly mode of the commercial liquid flow battery, and superposing the working electrode, the catholyte, the PP/PE/PP three-layer porous membrane, the lithium sulfur electrolyte and the lithium metal cathode in sequence in a glove box in an argon atmosphere to obtain the lithium-sulfur semi-flow battery.
and testing the performance of the battery in a battery test system, wherein the charge ~ discharge cut ~ off voltage is 1.8V ~ 2.6V, and the charge ~ discharge current density is 0.50 mA/cm.
example 3
a lithium-sulfur semi-flow battery with high energy density, high power density and long service life comprises a sulfur flow positive electrode area, a lithium metal negative electrode area and a diaphragm; the liquid sulfur positive region comprises a working electrode and lithium polysulfide catholyte; the working electrode comprises an active material capable of catalyzing the conversion of lithium polysulfide, a conductive agent, a binder and a current collector; the mass ratio of the active material capable of catalyzing the conversion of lithium polysulfide to the conductive agent to the binder is 8:1: 1; the conductive agent and the binder are common products of commercial batteries, preferably Super p is used as the conductive agent, and preferably polyvinylidene fluoride (PVDF) is used as the binder; the current collector is carbon paper; the active material capable of catalyzing the conversion of lithium polysulfide is a Ni/C composite material; the lithium polysulfide cathode electrolyte is formed by dissolving lithium polysulfide in lithium sulfur electrolyte, and the concentration of the lithium polysulfide is 0.1 mol/L; the lithium metal negative electrode region comprises a lithium metal negative electrode and lithium sulfur electrolyte, the lithium metal negative electrode is a lithium tin alloy (Li0.9Sn0.1), and the diaphragm is a three-layer porous diaphragm (PP/PE/PP); the solvent of the lithium-sulfur electrolyte of the embodiment is represented by the formula R (CH)2CH2O) n-R 'wherein n =6, R is ethyl, R' is methyl, the solute is lithium bis (fluorosulfonyl) imide, and the concentration of the lithium sulfur electrolyte is 1 mol/L.
The preparation process of the lithium-sulfur semi-flow battery of the embodiment specifically comprises the following steps:
A. the preparation method of the Ni/C composite material comprises the following specific steps:
(1) Adding the C conductive carrier graphene dispersion liquid (3 wt%) into a beaker filled with deionized water, and carrying out ultrasonic treatment for 5 hours to obtain a carbon-based carrier dispersion liquid with the concentration of 10 mg/mL;
(2) Adding nickel acetate into the carbon-based carrier dispersion liquid obtained in the step (1) according to the mass ratio of C to Ni of 15:1, and performing ultrasonic treatment for 1 hour to obtain a mixed dispersion liquid;
(3) Rapidly freezing the mixed dispersion liquid in the step (2) by using liquid nitrogen, and freeze-drying by using a freeze dryer to obtain mixed powder;
(4) placing the mixed powder in the step (3) in a tube furnace under the protection of Ar gas, heating to 900 ℃ at the speed of 5 ℃/min, calcining for 1 hour, and naturally cooling to obtain a Ni/C composite material;
B. the preparation method of the working electrode comprises the following specific steps:
(1) mixing and grinding 80 parts by weight of the active material Ni/C composite material capable of catalyzing the conversion of lithium polysulfide prepared in the step A and 10 parts by weight of conductive agent Super p to obtain mixed powder;
(2) Stirring and mixing the mixed powder obtained in the step (1) and 10 parts by weight of a binder polyvinylidene fluoride (PVDF), and coating the mixed slurry on a current collector; coating the slurry until the thickness of the current collector is 50 microns, and performing vacuum drying at 60 ℃ for 10 hours to remove the solvent to obtain a working electrode;
C. And C, preparing the lithium-sulfur semi-flow battery, namely using the working positive electrode obtained in the step B and the lithium polysulfide catholyte together as a liquid sulfur positive electrode area, using the lithium metal negative electrode and the lithium sulfur electrolyte as a lithium metal negative electrode area, assembling the lithium metal negative electrode and the lithium sulfur electrolyte together with a diaphragm into the battery according to the assembly mode of the commercial liquid flow battery, and stacking the working electrode, the catholyte, the three-layer porous diaphragm (PP/PE/PP), the lithium sulfur electrolyte and the lithium metal negative electrode in sequence in a glove box in an argon atmosphere to obtain the lithium-sulfur semi-flow battery.
testing the performance of the battery in a battery testing system, wherein the cut ~ off voltage of charge and discharge is 1.8V ~ 2.6V, and the current density of charge and discharge is 0.50mA cm-2。
example 4
A lithium-sulfur semi-flow battery with high energy density, high power density and long service life comprises a sulfur flow positive electrode area, a lithium metal negative electrode area and a diaphragm; the liquid sulfur positive region comprises a working electrode and lithium polysulfide catholyte; the working electrode comprises an active material capable of catalyzing the conversion of lithium polysulfide, a conductive agent, a binder and a current collector; can catalyze morethe mass ratio of the active material converted from the lithium sulfide, the conductive agent and the binder is 8:1: 1; the conductive agent and the binder are common products of commercial batteries, preferably Super p is used as the conductive agent, and preferably polyvinylidene fluoride (PVDF) is used as the binder; the current collector is a stainless steel mesh; the active material capable of catalyzing the conversion of lithium polysulfide is a Pt/C composite material; the lithium polysulfide cathode electrolyte is formed by dissolving lithium polysulfide in lithium sulfur electrolyte, and the concentration of the lithium polysulfide is 1 mol/L; the lithium metal negative electrode region comprises a lithium metal negative electrode and lithium sulfur electrolyte, the lithium metal negative electrode is lithium silicon alloy (Li0.9Si0.1), and the diaphragm is a three-layer porous diaphragm (PP/PE/PP); the solvent of the lithium-sulfur electrolyte of the embodiment is represented by the formula R (CH)2CH2o) n-R 'wherein n =6, R and R' are both methyl, the solute is lithium hexafluorophosphate, and the concentration of the lithium sulfur electrolyte is 1 mol/L.
the preparation process of the lithium-sulfur semi-flow battery of the embodiment specifically comprises the following steps:
A. The preparation method of the Pt/C composite material comprises the following specific steps:
(1) Adding the C conductive carrier graphene dispersion liquid (3 wt%) into a beaker filled with deionized water, and carrying out ultrasonic treatment for 3 hours to obtain a carbon-based carrier dispersion liquid with the concentration of 10 mg/mL;
(2) adding platinum acetate into the carbon-based carrier dispersion liquid obtained in the step (1) according to the mass ratio of C to Pt of 15:1, and performing ultrasonic treatment for 5 hours to obtain a mixed dispersion liquid;
(3) Rapidly freezing the mixed dispersion liquid in the step (2) by using liquid nitrogen, and freeze-drying by using a freeze dryer to obtain mixed powder;
(4) Placing the mixed powder in the step (3) in a tube furnace under the protection of Ar gas, heating to 800 ℃ at the speed of 5 ℃/min, calcining for 2 hours, and naturally cooling to obtain a Pt/C composite material;
B. The preparation method of the working electrode comprises the following specific steps:
(1) mixing and grinding 80 parts by weight of the active material Pt/C composite material capable of catalyzing the conversion of lithium polysulfide prepared in the step A and 10 parts by weight of conductive agent Super p to obtain mixed powder;
(2) stirring and mixing the mixed powder obtained in the step (1) and 10 parts by weight of a binder polyvinylidene fluoride (PVDF), and coating the mixed slurry on a current collector; coating the slurry until the thickness of the current collector is 30 microns, and performing vacuum drying at 60 ℃ for 15 hours to remove the solvent to obtain a working electrode;
C. And C, preparing the lithium-sulfur semi-flow battery, namely using the working positive electrode obtained in the step B and the lithium polysulfide catholyte together as a liquid sulfur positive electrode area, using the lithium metal negative electrode and the lithium sulfur electrolyte as a lithium metal negative electrode area, assembling the lithium metal negative electrode and the lithium sulfur electrolyte together with a diaphragm into the battery according to the assembly mode of the commercial liquid flow battery, and stacking the working electrode, the catholyte, the three-layer porous diaphragm (PP/PE/PP), the lithium sulfur electrolyte and the lithium metal negative electrode in sequence in a glove box in an argon atmosphere to obtain the lithium-sulfur semi-flow battery.
and testing the performance of the battery in a battery test system, wherein the charge ~ discharge cut ~ off voltage is 1.8V ~ 2.6V, and the charge ~ discharge current density is 0.50 mA/cm.
example 5
a lithium-sulfur semi-flow battery with high energy density, high power density and long service life comprises a sulfur flow positive electrode area, a lithium metal negative electrode area and a diaphragm; the liquid sulfur positive region comprises a working electrode and lithium polysulfide catholyte; the working electrode comprises an active material capable of catalyzing the conversion of lithium polysulfide, a conductive agent, a binder and a current collector; the mass ratio of the active material capable of catalyzing the conversion of lithium polysulfide to the conductive agent to the binder is 8:1: 1; the conductive agent and the binder are common products of commercial batteries, preferably Super p is used as the conductive agent, and preferably polyvinylidene fluoride (PVDF) is used as the binder; the current collector is a stainless steel mesh; the active material capable of catalyzing the conversion of lithium polysulfide is a Pt/C composite material; the lithium polysulfide cathode electrolyte is formed by dissolving lithium polysulfide in lithium sulfur electrolyte, and the concentration of the lithium polysulfide is 2 mol/L; the lithium metal negative electrode region comprises a lithium metal negative electrode and lithium sulfur electrolyte, the lithium metal negative electrode is a lithium copper alloy (Li0.9Cu0.1), and the diaphragm is a three-layer porous diaphragm (PP/PE/PP); the solvent of the lithium-sulfur electrolyte of the embodiment is represented by the formula R (CH)2CH2O) n-R 'wherein n =2, R and R' are both ethyl, the solute is lithium bistrifluoromethylsulfonimide, and the concentration of the lithium sulfur electrolyte is 1 mol/L.
The preparation process of the lithium-sulfur semi-flow battery of the embodiment specifically comprises the following steps:
A. The preparation method of the Pt/C composite material comprises the following specific steps:
(1) Adding the C conductive carrier acetylene black dispersion liquid (3 wt%) into a beaker filled with deionized water, and carrying out ultrasonic treatment for 1 hour to obtain a carbon-based carrier dispersion liquid with the concentration of 4 mg/mL;
(2) Adding platinum nitrate into the carbon-based carrier dispersion liquid in the step (1) according to the mass ratio of C to Pt of 10:1, and performing ultrasonic treatment for 3 hours to obtain a mixed dispersion liquid;
(3) rapidly freezing the mixed dispersion liquid in the step (2) by using liquid nitrogen, and freeze-drying by using a freeze dryer to obtain mixed powder;
(4) Placing the mixed powder in the step (3) in a tube furnace under the protection of Ar gas, heating to 900 ℃ at the speed of 5 ℃/min, calcining for 1 hour, and naturally cooling to obtain a Pt/C composite material;
B. The preparation method of the working electrode comprises the following specific steps:
(1) mixing and grinding 80 parts by weight of the Pt/C composite material which is the active material and can catalyze the conversion of lithium polysulfide and is prepared in the step A and 10 parts by weight of Super p which is a conductive agent to obtain mixed powder;
(2) Stirring and mixing the mixed powder obtained in the step (1) and 10 parts by weight of a binder polyvinylidene fluoride (PVDF), and coating the mixed slurry on a current collector; coating the slurry until the thickness of the current collector is 10 microns, and performing vacuum drying at 60 ℃ for 12 hours to remove the solvent to obtain a working electrode;
C. And C, preparing the lithium-sulfur semi-flow battery, namely using the working positive electrode obtained in the step B and the lithium polysulfide catholyte together as a liquid sulfur positive electrode area, using the lithium metal negative electrode and the lithium sulfur electrolyte as a lithium metal negative electrode area, assembling the lithium metal negative electrode and the lithium sulfur electrolyte together with a diaphragm into the battery according to the assembly mode of the commercial liquid flow battery, and stacking the working electrode, the catholyte, the three-layer porous diaphragm (PP/PE/PP), the lithium sulfur electrolyte and the lithium metal negative electrode in sequence in a glove box in an argon atmosphere to obtain the lithium-sulfur semi-flow battery.
and testing the performance of the battery in a battery test system, wherein the charge ~ discharge cut ~ off voltage is 1.8V ~ 2.6V, and the charge ~ discharge current density is 0.50 mA/cm.
Example 6
A lithium-sulfur semi-flow battery with high energy density, high power density and long service life comprises a sulfur flow positive electrode area, a lithium metal negative electrode area and a diaphragm; the liquid sulfur positive region comprises a working electrode and lithium polysulfide catholyte; the working electrode comprises an active material capable of catalyzing the conversion of lithium polysulfide, a conductive agent, a binder and a current collector; the mass ratio of the active material capable of catalyzing the conversion of lithium polysulfide to the conductive agent to the binder is 8:1: 1; the conductive agent and the binder are common products of commercial batteries, preferably Super p is used as the conductive agent, and preferably polyvinylidene fluoride (PVDF) is used as the binder; the current collector is a stainless steel mesh; the active material capable of catalyzing the conversion of lithium polysulfide is a Pt/C composite material; the lithium polysulfide cathode electrolyte is formed by dissolving lithium polysulfide in lithium sulfur electrolyte, and the concentration of the lithium polysulfide is 1 mol/L; the lithium metal negative electrode region comprises a lithium metal negative electrode and lithium sulfur electrolyte, the lithium metal negative electrode is lithium metal, and the diaphragm is a three-layer porous diaphragm (PP/PE/PP); the solvent of the lithium-sulfur electrolyte of the embodiment is represented by the formula R (CH)2CH2O) n-R 'wherein n =5, R is methyl, R' is ethyl, the solute is lithium difluorophosphate, and the concentration of the lithium sulfur electrolyte is 1 mol/L.
the preparation process of the lithium-sulfur semi-flow battery of the embodiment specifically comprises the following steps:
A. the preparation method of the Pt/C composite material comprises the following specific steps:
(1) Adding the C conductive carrier graphene dispersion liquid (3 wt%) into a beaker filled with deionized water, and carrying out ultrasonic treatment for 5 hours to obtain a carbon-based carrier dispersion liquid with the concentration of 1 mg/mL;
(2) Adding platinum nitrate into the carbon-based carrier dispersion liquid obtained in the step (1) according to the mass ratio of C to Pt of 5:1, and performing ultrasonic treatment for 1 hour to obtain a mixed dispersion liquid;
(3) Rapidly freezing the mixed dispersion liquid in the step (2) by using liquid nitrogen, and freeze-drying by using a freeze dryer to obtain mixed powder;
(4) Placing the mixed powder in the step (3) in a tube furnace under the protection of Ar gas, heating to 700 ℃ at a speed of 5 ℃/min, calcining for 3 hours, and naturally cooling to obtain a Pt/C composite material;
B. The preparation method of the working electrode comprises the following specific steps:
(1) Mixing and grinding 80 parts by weight of the active material Pt/C composite material capable of catalyzing the conversion of lithium polysulfide prepared in the step A and 10 parts by weight of conductive agent Super p to obtain mixed powder;
(2) stirring and mixing the mixed powder obtained in the step (1) and 10 parts by weight of a binder polyvinylidene fluoride (PVDF), and coating the mixed slurry on a current collector; coating the slurry until the thickness of the current collector is 500 micrometers, and vacuum-drying at 60 ℃ for 24 hours to remove the solvent to obtain a working electrode;
C. and C, preparing the lithium-sulfur semi-flow battery, namely using the working positive electrode obtained in the step B and the lithium polysulfide catholyte together as a liquid sulfur positive electrode area, using the lithium metal negative electrode and the lithium sulfur electrolyte as a lithium metal negative electrode area, assembling the lithium metal negative electrode and the lithium sulfur electrolyte together with a diaphragm into the battery according to the assembly mode of the commercial liquid flow battery, and stacking the working electrode, the catholyte, the three-layer porous diaphragm (PP/PE/PP), the lithium sulfur electrolyte and the lithium metal negative electrode in sequence in a glove box in an argon atmosphere to obtain the lithium-sulfur semi-flow battery.
and testing the performance of the battery in a battery test system, wherein the charge ~ discharge cut ~ off voltage is 1.8V ~ 2.6V, and the charge ~ discharge current density is 0.50 mA/cm.
Example 7
A lithium-sulfur semi-flow battery with high energy density, high power density and long service life comprises a sulfur flow positive electrode area, a lithium metal negative electrode area and a diaphragm; the liquid sulfur positive region comprises a working electrode and lithium polysulfide catholyte; the working electrode comprises an active material capable of catalyzing the conversion of lithium polysulfide, a conductive agent, a binder and a current collector; the mass ratio of the active material capable of catalyzing the conversion of lithium polysulfide to the conductive agent to the binder is 8:1: 1; the conductive agent and the binder are common products of commercial batteries, preferably Super p is used as the conductive agent, and preferably polyvinylidene fluoride (PVDF) is used as the binder; the current collector is a stainless steel mesh; the active material capable of catalyzing the conversion of lithium polysulfide is Pt3Ni/C complexcombining materials; the lithium polysulfide cathode electrolyte is formed by dissolving lithium polysulfide in lithium sulfur electrolyte, and the concentration of the lithium polysulfide is 1 mol/L; the lithium metal negative electrode region comprises a lithium metal negative electrode and lithium sulfur electrolyte, the lithium metal negative electrode is lithium metal, and the diaphragm is a three-layer porous diaphragm (PP/PE/PP); the solvent of the lithium-sulfur electrolyte of the embodiment is represented by the formula R (CH)2CH2O) n-R 'wherein n =2, R and R' are both ethyl, the solute is lithium bistrifluoromethylsulfonimide, and the concentration of the lithium sulfur electrolyte is 1 mol/L.
the preparation process of the lithium-sulfur semi-flow battery of the embodiment specifically comprises the following steps:
A、Pt3The preparation method of the Ni/C composite material comprises the following specific steps:
(1) adding a C conductive carrier Super p with the weight of 10mg into a round-bottom flask containing 10mLDMF, and carrying out ultrasonic treatment for 1 hour to obtain a carbon-based carrier dispersion liquid with the concentration of 1 mg/mL;
(2) Mixing platinum diacetone (Pt (acac)2) Nickel diacetone (Ni (acac)2) Push button Pt (acac)2:Ni(acac)2adding C into the carbon-based carrier dispersion liquid obtained in the step (1) at a mass ratio of 8:8:20, adding benzoic acid, adding the benzoic acid according to a mass ratio of diacetone platinum to benzoic acid of 8:50, and performing ultrasonic treatment for 1 hour to obtain a mixed dispersion liquid;
(3) heating the mixed dispersion liquid in the step (2) in a constant-temperature water bath at 150 ℃, and reacting for 24 hours;
(4) centrifugally separating the product obtained in the step (3) to obtain Pt3a Ni/C composite material;
B. the preparation method of the working electrode comprises the following specific steps:
(1) 80 parts by weight of active material Pt which is prepared in the step A and can catalyze the conversion of lithium polysulfide3Mixing the Ni/C composite material and 10 parts by weight of conductive agent Super p, and grinding to obtain mixed powder;
(2) Stirring and mixing the mixed powder obtained in the step (1) and 10 parts by weight of a binder polyvinylidene fluoride (PVDF) solution, and coating the mixed slurry on a current collector; coating the slurry until the thickness of the current collector is 50 microns, and performing vacuum drying at 60 ℃ for 24 hours to remove the solvent to obtain a working electrode;
C. And C, preparing the lithium-sulfur semi-flow battery, namely using the working positive electrode obtained in the step B and the lithium polysulfide catholyte together as a liquid sulfur positive electrode area, using the lithium metal negative electrode and the lithium sulfur electrolyte as a lithium metal negative electrode area, assembling the lithium metal negative electrode and the lithium sulfur electrolyte together with a diaphragm into the battery according to the assembly mode of the commercial liquid flow battery, and stacking the working electrode, the catholyte, the three-layer porous diaphragm (PP/PE/PP), the lithium sulfur electrolyte and the lithium metal negative electrode in sequence in a glove box in an argon atmosphere to obtain the lithium-sulfur semi-flow battery.
and testing the performance of the battery in a battery test system, wherein the charge ~ discharge cut ~ off voltage is 1.8V ~ 2.6V, and the charge ~ discharge current density is 0.50 mA/cm.
example 8
A lithium-sulfur semi-flow battery with high energy density, high power density and long service life comprises a sulfur flow positive electrode area, a lithium metal negative electrode area and a diaphragm; the liquid sulfur positive region comprises a working electrode and lithium polysulfide catholyte; the working electrode comprises an active material capable of catalyzing the conversion of lithium polysulfide, a conductive agent, a binder and a current collector; the mass ratio of the active material capable of catalyzing the conversion of lithium polysulfide to the conductive agent to the binder is 8:1: 1; the conductive agent and the binder are common products of commercial batteries, preferably Super p is used as the conductive agent, and preferably polyvinylidene fluoride (PVDF) is used as the binder; the current collector is a stainless steel mesh; the active material capable of catalyzing the conversion of lithium polysulfide is Pt3a Ni/C composite material; the lithium polysulfide cathode electrolyte is formed by dissolving lithium polysulfide in lithium sulfur electrolyte, and the concentration of the lithium polysulfide is 1 mol/L; the lithium metal negative electrode region comprises a lithium metal negative electrode and lithium sulfur electrolyte, the lithium metal negative electrode is lithium metal, and the diaphragm is a three-layer porous diaphragm (PP/PE/PP); the solvent of the lithium-sulfur electrolyte of the embodiment is represented by the formula R (CH)2CH2O) n-R 'wherein n =1, R and R' are both methyl, the solute is lithium difluorooxalato borate, and the concentration of the lithium sulfur electrolyte is 1 mol/L.
The preparation process of the lithium-sulfur semi-flow battery of the embodiment specifically comprises the following steps:
A、Pt3Ni/C composite materialThe preparation method comprises the following specific steps:
(1) Adding a C conductive carrier CNT with the weight of 200mg into a round-bottom flask containing 20mLDMF, and carrying out ultrasonic treatment for 5 hours to obtain carbon-based carrier dispersion liquid with the concentration of 10 mg/mL;
(2) Mixing platinum diacetone (Pt (acac)2) Nickel diacetone (Ni (acac)2) Push button Pt (acac)2:Ni(acac)2Adding C into the carbon-based carrier dispersion liquid obtained in the step (1) at a mass ratio of 24:8:60, adding benzoic acid, adding the benzoic acid according to a mass ratio of diacetone platinum to benzoic acid of 8:60, and performing ultrasonic treatment for 5 hours to obtain a mixed dispersion liquid;
(3) heating the mixed dispersion liquid in the step (2) in a constant-temperature water bath at 160 ℃, and reacting for 22 hours;
(4) Centrifugally separating the product obtained in the step (3) to obtain Pt3a Ni/C composite material;
B. The preparation method of the working electrode comprises the following specific steps:
(1) 80 parts by weight of active material Pt which is prepared in the step A and can catalyze the conversion of lithium polysulfide3Mixing the Ni/C composite material and 10 parts by weight of conductive agent Super p, and grinding to obtain mixed powder;
(2) Stirring and mixing the mixed powder obtained in the step (1) and 10 parts by weight of a binder polyvinylidene fluoride (PVDF), and coating the mixed slurry on a current collector; coating the slurry until the thickness of the current collector is 500 micrometers, and vacuum-drying at 60 ℃ for 24 hours to remove the solvent to obtain a working electrode;
C. And C, preparing the lithium-sulfur semi-flow battery, namely using the working positive electrode obtained in the step B and the lithium polysulfide catholyte together as a liquid sulfur positive electrode area, using the lithium metal negative electrode and the lithium sulfur electrolyte as a lithium metal negative electrode area, assembling the lithium metal negative electrode and the lithium sulfur electrolyte together with a diaphragm into the battery according to the assembly mode of the commercial liquid flow battery, and stacking the working electrode, the catholyte, the three-layer porous diaphragm (PP/PE/PP), the lithium sulfur electrolyte and the lithium metal negative electrode in sequence in a glove box in an argon atmosphere to obtain the lithium-sulfur semi-flow battery.
and testing the performance of the battery in a battery test system, wherein the charge ~ discharge cut ~ off voltage is 1.8V ~ 2.6V, and the charge ~ discharge current density is 0.50 mA/cm.
Example 9
A lithium-sulfur semi-flow battery with high energy density, high power density and long service life comprises a sulfur flow positive electrode area, a lithium metal negative electrode area and a diaphragm; the liquid sulfur positive region comprises a working electrode and lithium polysulfide catholyte; the working electrode comprises an active material capable of catalyzing the conversion of lithium polysulfide, a conductive agent, a binder and a current collector; the mass ratio of the active material capable of catalyzing the conversion of lithium polysulfide to the conductive agent to the binder is 8:1: 1; the conductive agent and the binder are common products of commercial batteries, preferably Super p is used as the conductive agent, and preferably polyvinylidene fluoride (PVDF) is used as the binder; the current collector is a stainless steel mesh; the active material capable of catalyzing the conversion of lithium polysulfide is Pt3a Ni/C composite material; the lithium polysulfide cathode electrolyte is formed by dissolving lithium polysulfide in lithium sulfur electrolyte, and the concentration of the lithium polysulfide is 1 mol/L; the lithium metal negative electrode region comprises a lithium metal negative electrode and lithium sulfur electrolyte, the lithium metal negative electrode is lithium metal, and the diaphragm is a three-layer porous diaphragm (PP/PE/PP); the solvent of the lithium-sulfur electrolyte of the embodiment is represented by the formula R (CH)2CH2o) n-R 'wherein n =2, R and R' are both ethyl, the solute is lithium difluorophosphate, and the concentration of the lithium sulfur electrolyte is 1 mol/L.
The preparation process of the lithium-sulfur semi-flow battery of the embodiment specifically comprises the following steps:
A、Pt3The preparation method of the Ni/C composite material comprises the following specific steps:
(1) Adding carbon black of a C conductive carrier with the weight of 40mg into a round-bottom flask containing 20mL of DMF, and carrying out ultrasonic treatment for 2 hours to obtain carbon-based carrier dispersion liquid with the concentration of 2 mg/mL;
(2) Mixing platinum diacetone (Pt (acac)2) Nickel diacetone (Ni (acac)2) Push button Pt (acac)2:Ni(acac)2Adding C into the carbon-based carrier dispersion liquid obtained in the step (1) at a mass ratio of 16:8:40, adding benzoic acid, adding the benzoic acid according to a mass ratio of diacetone platinum to benzoic acid of 8:61, and performing ultrasonic treatment for 3 hours to obtain a mixed dispersion liquid;
(3) Heating the mixed dispersion liquid in the step (2) in a constant-temperature water bath at 170 ℃, and reacting for 20 hours;
(4) centrifugally separating the product obtained in the step (3) to obtain Pt3a Ni/C composite material;
B. the preparation method of the working electrode comprises the following specific steps:
(1) 80 parts by weight of active material Pt which is prepared in the step A and can catalyze the conversion of lithium polysulfide3Mixing the Ni/C composite material and 10 parts by weight of conductive agent Super p, and grinding to obtain mixed powder;
(2) stirring and mixing the mixed powder obtained in the step (1) and 10 parts by weight of a binder polyvinylidene fluoride (PVDF), and coating the mixed slurry on a current collector; coating the slurry until the thickness of the current collector is 50 microns, and performing vacuum drying at 60 ℃ for 24 hours to remove the solvent to obtain a working electrode;
C. And C, preparing the lithium-sulfur semi-flow battery, namely using the working anode obtained in the step B and the lithium polysulfide catholyte together as a liquid sulfur anode region, using the lithium metal cathode and the lithium sulfur electrolyte as a lithium metal cathode region, assembling the lithium metal cathode and the lithium sulfur electrolyte together with a diaphragm into the battery according to the assembly mode of the commercial liquid flow battery, and stacking the working electrode, the catholyte, the three-layer porous diaphragm (PP/PE/PP), the conventional lithium sulfur electrolyte and the lithium metal cathode in sequence in a glove box in an argon atmosphere to obtain the lithium-sulfur semi-flow battery.
and testing the performance of the battery in a battery test system, wherein the charge ~ discharge cut ~ off voltage is 1.8V ~ 2.6V, and the charge ~ discharge current density is 0.50 mA/cm.
FIG. 2 shows Pt in example 93SEM image of Ni/C composite material, from FIG. 1, Pt of several nm in size can be seen3ni is uniformly loaded on the carbon black, which is beneficial to increasing the conductivity of the composite material and increasing the contact area with lithium polysulfide, thereby enhancing the accelerating capacity of the composite material on the conversion of the lithium polysulfide.
FIG. 3 shows Pt in example 93The charge-discharge curve of the lithium-sulfur semi-flow battery using the Ni/C composite material as the working electrode can be seen from the graph, and the charge-discharge curve shows the same charge-discharge platform as the lithium-sulfur battery.
FIG. 4 shows Pt in example 93cycle performance of lithium-sulfur semi-flow battery with Ni/C composite material as working electrode can be seen from the figure, Pt3the lithium-sulfur semi-flow battery with the Ni/C composite material as the working electrode has higher specific capacity, is kept about 550mAh/g, and is stable in circulation, because the Pt is used as the material3the Ni/C composite material has excellent and stable catalytic activity for the conversion of lithium polysulfide.
Claims (10)
1. The lithium-sulfur semi-flow battery is characterized by comprising a liquid sulfur positive electrode area, a lithium metal negative electrode area and a diaphragm.
2. The lithium-sulfur semi-flow battery of claim 1, wherein the positive flow sulfur region comprises a working electrode, a lithium polysulfide catholyte.
3. The lithium-sulfur semi-flow battery of claim 2, wherein the working electrode comprises an active material, a conductive agent, a binder, a current collector; the mass ratio of the active material, the conductive agent and the binder is 8:1: 1.
4. The lithium-sulfur semi-flow battery of claim 3, wherein the active material is a Ni/C composite, a Pt/C composite, or Pt3a Ni/C composite material; the conductive agent and the binder are common products of commercial batteries; the current collector is aluminum foil, stainless steel mesh or carbon paper.
5. The lithium-sulfur semi-flow battery according to claim 2, wherein the lithium polysulfide catholyte is obtained by dissolving lithium polysulfide in lithium sulfur electrolyte, and the concentration of the lithium polysulfide is 0.1 mol/L-2 mol/L; the solvent of the lithium-sulfur electrolyte is R (CH)2CH2O) n-R 'wherein n =1-6, R and R' are methyl or ethyl, the solute is lithium difluorooxalato borate, lithium bistrifluoromethylsulfonylimide, lithium difluorosulfonylimide, lithium difluorophosphate or lithium hexafluorophosphate, and the concentration of the lithium sulfur electrolyte is 1 mol/L.
6. the lithium-sulfur semi-flow battery according to claim 1, wherein the lithium metal negative electrode region comprises a lithium metal negative electrode, a lithium sulfur electrolyte, the lithium metal negative electrode is lithium metal or a lithium metal alloy, and the lithium metal alloy is a lithium tin alloy, a lithium silicon alloy or a lithium copper alloy; the solvent of the lithium-sulfur electrolyte is R (CH)2CH2O) n-R 'wherein n =1-6, R and R' are methyl or ethyl, the solute is lithium difluorooxalato borate, lithium bistrifluoromethylsulfonylimide, lithium difluorosulfonylimide, lithium difluorophosphate or lithium hexafluorophosphate, and the concentration of the lithium sulfur electrolyte is 1 mol/L.
7. The lithium-sulfur semi-flow battery according to claim 1, wherein the separator is PP, PE or PP/PE/PP.
8. the lithium-sulfur semi-flow battery according to claim 4, wherein the preparation method of the Ni/C composite material comprises the following specific steps:
(1) carrying out ultrasonic treatment on a C conductive carrier and deionized water for 1 ~ 5 hours to obtain a carbon ~ based carrier dispersion liquid with the concentration of 1 ~ 10mg/mL, wherein the C conductive carrier is one of graphene, Super p, carbon black, acetylene black and CNT;
(2) adding nickel acetate or nickel nitrate into the carbon ~ based carrier dispersion liquid obtained in the step (1) according to the mass ratio of C to Ni of 5 ~ 15:1, and performing ultrasonic treatment for 1 ~ 5 hours to obtain a mixed dispersion liquid;
(3) Freezing the mixed dispersion liquid obtained in the step (2) by using liquid nitrogen, and carrying out freeze drying to obtain mixed powder;
(4) and (3) under the protection of Ar gas, heating the mixed powder in the step (3) to 700 ~ 900 ℃ at a heating rate of 5 ℃/min, calcining for 1 ~ 3 hours, and naturally cooling to obtain the Ni/C composite material.
9. the lithium-sulfur semi-flow battery according to claim 8, wherein the preparation method of the Pt/C composite material is the same as the preparation method of the Ni/C composite material, and the nickel acetate or the nickel nitrate in the step (2) is replaced by platinum acetate or platinum nitrate.
10. the lithium-sulfur semi-flow battery of claim 4, wherein Pt3the preparation method of the Ni/C composite material comprises the following specific steps:
(1) adding a C conductive carrier into DMF (dimethyl formamide), and carrying out ultrasonic treatment for 1 ~ 5 hours to obtain a carbon ~ based carrier dispersion liquid with the concentration of 1 ~ 10mg/mL, wherein the C conductive carrier is one of graphene, Super p, carbon black, acetylene black and CNT;
(2) adding platinum diacetylacetonate and nickel diacetylacetonate into the carbon ~ based carrier dispersion liquid obtained in the step (1) according to the mass ratio of the platinum diacetylacetonate to the nickel diacetylacetonate to C of 8:8:20 ~ 24:8:60, adding benzoic acid, adding the benzoic acid according to the mass ratio of the platinum diacetylacetonate to the benzoic acid of 8:50 ~ 70, and performing ultrasonic treatment for 1 ~ 5 hours to obtain a mixed dispersion liquid;
(3) heating the mixed dispersion liquid in the step (2) in a constant ~ temperature water bath at the temperature of 150 ~ 170 ℃, and reacting for 20 ~ 24 hours;
(4) centrifugally separating the product obtained in the step (3), and drying to obtain Pt3a Ni/C composite material.
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