CN111769282B - Application method of water-based binder in magnesium-sulfur battery - Google Patents
Application method of water-based binder in magnesium-sulfur battery Download PDFInfo
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- SMDQFHZIWNYSMR-UHFFFAOYSA-N sulfanylidenemagnesium Chemical compound S=[Mg] SMDQFHZIWNYSMR-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000011230 binding agent Substances 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000011593 sulfur Substances 0.000 claims abstract description 26
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 26
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 22
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000007774 positive electrode material Substances 0.000 claims abstract description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003792 electrolyte Substances 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 11
- 229920000161 Locust bean gum Polymers 0.000 claims abstract description 9
- 235000010420 locust bean gum Nutrition 0.000 claims abstract description 9
- 239000000711 locust bean gum Substances 0.000 claims abstract description 9
- 229910052786 argon Inorganic materials 0.000 claims abstract description 8
- 239000006258 conductive agent Substances 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 13
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 12
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 239000006230 acetylene black Substances 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 229910003002 lithium salt Inorganic materials 0.000 claims description 6
- 159000000002 lithium salts Chemical class 0.000 claims description 6
- IWCVDCOJSPWGRW-UHFFFAOYSA-M magnesium;benzene;chloride Chemical compound [Mg+2].[Cl-].C1=CC=[C-]C=C1 IWCVDCOJSPWGRW-UHFFFAOYSA-M 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- XDBOBNVQEBSKFO-UHFFFAOYSA-N magnesium;di(propan-2-yl)azanide Chemical compound CC(C)N(C(C)C)[Mg]N(C(C)C)C(C)C XDBOBNVQEBSKFO-UHFFFAOYSA-N 0.000 claims description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- DKQZQULUUSZOPS-UHFFFAOYSA-J [Al+3].[Cl-].[Cl-].[Cl-].Cl[Mg]c1ccccc1 Chemical compound [Al+3].[Cl-].[Cl-].[Cl-].Cl[Mg]c1ccccc1 DKQZQULUUSZOPS-UHFFFAOYSA-J 0.000 claims description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002296 pyrolytic carbon Substances 0.000 claims description 4
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- TVQJXDILVIOKPR-UHFFFAOYSA-K [Al](Cl)(Cl)Cl.C(C)(C)N(C(C)C)[Mg]N(C(C)C)C(C)C Chemical compound [Al](Cl)(Cl)Cl.C(C)(C)N(C(C)C)[Mg]N(C(C)C)C(C)C TVQJXDILVIOKPR-UHFFFAOYSA-K 0.000 claims description 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000012448 Lithium borohydride Substances 0.000 claims description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 2
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 2
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 abstract description 22
- 229910052749 magnesium Inorganic materials 0.000 abstract description 20
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 239000013543 active substance Substances 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 abstract description 5
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract 1
- 239000002033 PVDF binder Substances 0.000 description 9
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- -1 V)2O Inorganic materials 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 229920002125 Sokalan® Polymers 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 239000004584 polyacrylic acid Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229920006125 amorphous polymer Polymers 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000011883 electrode binding agent Substances 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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Classifications
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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
- H01M4/621—Binders
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/46—Alloys based on magnesium or aluminium
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses an application method of a water-based binder in a magnesium-sulfur battery, relating to the field of rechargeable magnesium-sulfur batteries, wherein the binder is locust bean gum or sodium polyacrylate, and a binder aqueous solution, a sulfur positive electrode material and a carbon conductive agent are uniformly mixed and coated on a current collector; and drying and tabletting, then transferring the dried and tabletted sheet into an argon glove box, adding electrolyte into the argon glove box by taking metal magnesium as a negative electrode, and assembling the magnesium-sulfur battery. The two binders are dissolved in water, can be used as solvents, have the advantages of low price, easily obtained raw materials, environmental friendliness, excellent binding performance and high anode sulfur capacity, can improve the active substance capacity of the anode of the magnesium-sulfur battery, ensures the stability of the anode, and realizes the excellent electrochemical performance of the magnesium-sulfur battery.
Description
Technical Field
The invention relates to the field of rechargeable magnesium-sulfur batteries, in particular to an application method of a water-based binder in a magnesium-sulfur battery.
Background
The magnesium is in the diagonal position with lithium in the periodic table of elements, and the ionic radius is similar to that of lithiumThe chemical properties are similar. Due to the characteristics of positive divalent ions of Mg, magnesium has very high mass energy density (2205mAh/g) and volume energy density (3833 mAh/cm)3) (ii) a Magnesium element has very abundant content (1.5 wt%) in earth crust, and is about 104 times of lithium in the eighth rank, so that the price is low; the magnesium cathode does not generate dendrite in the electrodeposition process, is safe and reliable, and the rechargeable magnesium battery taking magnesium as the cathode becomes a research hotspot of a novel battery system.
The feasibility of rechargeable magnesium batteries was first proposed by Gregory et al in 1990 (Gregory T D, Hoffman R J, Winterton, Development of an organic secondary magnesium battery, J.Electrochem. Soc.,137(1990) 775-780). In 2000, the research of Aurbach et al realized a major breakthrough in the field of rechargeable magnesium batteries (Aurbach D, Lu Z, Schechter A, et al. protocol systems for rechargeable magnesium batteries, Nature,2000,407: 724-. The positive electrode material of rechargeable magnesium battery is transition metal oxide (such as V)2O，MoO3，MnO2Etc.), transition metal sulfides (e.g., TiS)2MoS, etc.), polyanionic phosphate materials and silicate materials (e.g., MgMnSiO)4，MgFeSiO4) And the like. However, the problems of very slow kinetic intercalation, low intercalation amount, high overpotential, serious attenuation under multiple cycles and the like exist, so that the research of the magnesium cathode material is in a bottleneck. Therefore, the development of positive electrode materials with good reversibility, good safety performance, high capacity, high voltage and long cycle life is one of the main development directions of rechargeable magnesium batteries.
The elemental sulfur has the advantages of high theoretical specific capacity (1672mAh/g), low cost, environmental protection and the like, and can be used as a positive electrode material of a high-performance secondary battery. The magnesium-sulfur battery system which is composed of elemental sulfur as a positive active material and metal magnesium as a battery negative electrode has the advantages of high energy density, low price, safety and the like compared with other chemical power sources, has good development prospect in the field of heavy-load energy storage and electricity storage, particularly becomes the most potential power battery system under the era background of high-speed development of the new energy automobile industry, and has huge application prospect.
The conductivity of sulfur is poor, and the interface of a sulfur positive electrode is unstable and the long-term circulation performance is poor when the sulfur loading is high; the loading amount and the compaction density of sulfur in the positive pole piece are low, so that the energy density of the magnesium-sulfur battery is greatly reduced, and the market application of the magnesium-sulfur battery is limited. As an important component of the sulfur anode material, the application of the high-performance binder can well bind the active substance and the current collector, and is beneficial to increasing the active substance loading capacity; the volume effect of the sulfur material in the buffer cycle maintains the positive electrode structure, thereby enabling the battery to exhibit excellent cycle performance. However, the binder has problems of environmental unfriendliness, high price and the like.
Therefore, the technical personnel in the field are dedicated to develop a binder which can be applied to a magnesium-sulfur battery, has stable sulfur positive electrode interface, good long-term cycle performance, no toxicity and harm, low price, safety and environmental protection at high sulfur loading.
Disclosure of Invention
In view of the above defects in the prior art, the invention aims to solve the technical problem of finding a binder which can be applied to a magnesium-sulfur battery, has a stable sulfur positive electrode interface at high sulfur loading, has good long-term cycle performance, is nontoxic and harmless, is low in price, and is safe and environment-friendly.
In order to achieve the purpose, the invention provides an application method of a water-based binder in a magnesium-sulfur battery, wherein the binder is locust bean gum or sodium polyacrylate, and the application method comprises the following steps:
step 2, drying the current collector in an oven at 50-100 ℃ to manufacture a pole piece, tabletting under the pressure of 0.2-2.5 MPa, drying in vacuum at 50-130 ℃ for 3-24 hours, and transferring to an argon glove box;
and 3, taking the metal magnesium as a negative electrode, and adding an electrolyte to assemble the magnesium-sulfur battery.
Further, the mass ratio of the binder to the sulfur positive electrode material to the carbon conductive agent in the step 1 is 6-9: 0.5-2: 0.4 to 2.5.
Further, the sulfur positive electrode material in the step 1 contains carbon, the mass content of the carbon is 0-65%, and the carbon is at least one of microporous carbon, mesoporous carbon, macroporous carbon and pyrolytic carbon; the carbon conductive agent is acetylene black.
Further, the current collector in step 1 is any one of copper, aluminum or nickel.
Further, the electrolyte in step 3 is Mg (AlCl)2BuEt)2And any one of phenylmagnesium chloride-aluminum trichloride or bis (diisopropylamino) magnesium-aluminum trichloride, wherein the concentration of magnesium ions in the electrolyte is 0.1-2.0 mol/L.
Further, in the phenylmagnesium chloride-aluminum trichloride, the molar ratio of the phenylmagnesium chloride to the aluminum trichloride is 3-0.1; in the bis (diisopropylamino) magnesium-aluminum trichloride, the molar ratio of bis (diisopropylamino) magnesium to aluminum trichloride is 3-0.1.
Further, the electrolyte contains magnesium chloride.
Further, the molar ratio of either phenylmagnesium chloride or bis (diisopropylamino) magnesium chloride to magnesium chloride is 5 to 0.1.
Further, the ether is at least one of tetrahydrofuran, 2-methyltetrahydrofuran, 1, 3-dioxolane, diethyl ether, ethylene glycol dimethyl ether and tetraethylene glycol dimethyl ether.
Further, the electrolyte in step 3 contains a lithium salt, the lithium salt is at least one of lithium trifluoromethanesulfonate, lithium chloride, lithium fluoride, lithium bromide, lithium nitrate and lithium borohydride, and the concentration of the lithium salt is 0.01-2.0 mol/L.
The invention has the following technical effects:
1) locust bean gum and sodium polyacrylate are used as binders of the magnesium-sulfur battery, a stable porous structure can be formed in a sulfur positive electrode, and the sulfur positive electrode has strong mechanical adhesion and adaptability to active substances and current collectors, can be used for coating positive electrode slurry with high sulfur loading capacity, and can ensure that no crack occurs after drying; a layer of gel protective film can be formed on the surface of the sulfur anode, and the gel protective film has certain mechanical strength; can avoid the loss of active substances, can adsorb polysulfide ions and inhibit the dissolution of discharge intermediate products;
2) the 3D network structure can be formed in the positive electrode by the fracture and crosslinking of the functional groups, so that the volume expansion is inhibited, the stability of the positive electrode is ensured, and the excellent electrochemical performance of the magnesium-sulfur battery is realized;
3) the locust bean gum has a large number of-OH, -COOH and other strong hydrophilic groups, and the active functional groups of the locust bean gum can promote electrochemical reaction; binding to the surface of sulphur, carbon particles and collectors by physical and especially chemical forces;
4) the sodium polyacrylate is an amorphous polymer and can form a uniform mixture with the active substance, so that the surface of the electrode is uniformly covered; in the crosslinking process, a large number of macromolecular ions COO-and micromolecular ions Na + are generated, and attraction of electrostatic force exists near a macromolecular chain, so that the macromolecular chain has good mechanical property;
5) different from a commercial polyvinylidene fluoride (PVDF) binder which can only be dissolved in an organic solvent, the locust bean gum, the sodium polyacrylate and the solvent water are nontoxic and harmless substances, are low in price, safe and environment-friendly, can improve the environmental protection performance of the magnesium-sulfur battery, and is superior to the magnesium-sulfur battery assembled by taking the PVDF as a positive electrode binder in the aspect of electrochemical performance.
The conception, the specific structure and the technical effects of the present invention will be further described with reference to the accompanying drawings to fully understand the objects, the features and the effects of the present invention.
Drawings
FIG. 1 is a discharge capacity-cycle number relationship curve of a magnesium-sulfur battery according to a preferred embodiment of the present invention;
FIG. 2 is a graph showing discharge capacity versus cycle number of a magnesium-sulfur battery according to another preferred embodiment of the present invention;
FIG. 3 is a discharge capacity-cycle number relationship curve of a magnesium-sulfur battery according to a comparative example of the present invention;
fig. 4 is a discharge capacity-cycle number relationship curve of a magnesium-sulfur battery according to another comparative example of the present invention.
Detailed Description
The technical contents of the preferred embodiments of the present invention will be more clearly and easily understood by referring to the drawings attached to the specification. The present invention may be embodied in many different forms of embodiments and the scope of the invention is not limited to the embodiments set forth herein.
Example 1
Mixing a sulfur-microporous carbon positive electrode material (the mass fraction of sulfur is 55.1%), acetylene black and locust bean gum (water is a solvent) in a mass ratio of 8: 1: 1, fully and uniformly mixing, coating on a copper current collector, drying in a 70 ℃ oven to prepare a pole piece, tabletting under the pressure of 1 MPa, vacuum-drying for 8 hours at the temperature of 80 ℃, transferring into an argon glove box, taking metal magnesium as a negative electrode, and adding 0.4mol/L (phenylmagnesium chloride)2And (4) assembling aluminum chloride and 1.0mol/L lithium chloride/ether electrolyte into the magnesium-sulfur battery. And (4) carrying out constant-current charge and discharge performance test on a battery test system.
As shown in fig. 1, a relationship diagram of the discharge capacity and the cycle number of the magnesium-sulfur battery is shown when sulfur-microporous carbon is used as a positive electrode material and polyacrylic acid is used as a binder, and it can be seen that the first discharge capacity of the battery is 854.9mAh/g, the discharge capacity for 200 cycles is 348.1mAh/g, the discharge capacity retention rate is 40.7%, which is much higher than the cycle stability of the magnesium-sulfur battery when polyvinylidene fluoride is used as a binder in comparative example 1 under the same condition, and the capacity after 200 cycles is about 183.0 mAh/g.
Example 2
Mixing a sulfur-pyrolytic carbon cathode material (the mass fraction of sulfur is 47.3%), acetylene black and polyacrylic acid (water is used as a solvent) in a mass ratio of 8: 1: 1, fully and uniformly mixing, coating on a copper current collector, drying in a 70 ℃ oven to prepare a pole piece, tabletting under the pressure of 1 MPa, vacuum-drying for 8 hours at the temperature of 80 ℃, transferring into an argon glove box, taking metal magnesium as a negative electrode, and adding 0.2mol/L of bis (diisopropylamino) magnesium- (magnesium chloride)2And (4) assembling aluminum trichloride and 1.0mol/L lithium chloride/tetrahydrofuran electrolyte into the magnesium-sulfur battery. And (4) carrying out constant-current charge and discharge performance test on a battery test system.
As shown in fig. 2, a relation diagram of discharge capacity and cycle number of the magnesium-sulfur battery when sulfur-pyrolytic polyacrylonitrile is used as a positive electrode material and polyacrylic acid is used as a binder shows that the first discharge capacity of the battery is 622.1mAh/g, the second discharge capacity is 677.9mAh/g, the cycle 50 discharge capacity is 416.0mAh/g, the discharge capacity retention rate is 61.4%, which is far higher than the cycle stability of the magnesium-sulfur battery when polyvinylidene fluoride is used as a binder in comparative example 2 under the same condition, and the capacity after 50 cycles is higher than about 228.0 mAh/g.
Comparative example 1
The method comprises the following steps of (1) preparing a sulfur-microporous carbon positive electrode material (mass fraction of sulfur is 55.1%), acetylene black, polyvinylidene fluoride (N-methylpyrrolidone is used as a solvent) in a mass ratio of (8): 1: 1, fully and uniformly mixing, coating on a copper current collector, drying in a 70 ℃ oven to prepare a pole piece, tabletting under the pressure of 1 MPa, vacuum-drying for 8 hours at the temperature of 80 ℃, transferring into an argon glove box, taking metal magnesium as a negative electrode, and adding 0.4mol/L (phenylmagnesium chloride)2And (4) assembling aluminum chloride and 1.0mol/L lithium chloride/ether electrolyte into the magnesium-sulfur battery. And (4) carrying out constant-current charge and discharge performance test on a battery test system.
As shown in fig. 3, a relationship graph of the discharge capacity and the cycle number of the magnesium-sulfur battery when the sulfur-microporous carbon is used as the positive electrode material and the polyvinylidene fluoride is used as the binder shows that the first discharge capacity of the battery is 802.7mAh/g, the discharge capacity for 200 cycles is 165.0mAh/g, the discharge capacity retention rate is 20.6%, which is far lower than the cycle stability of the magnesium-sulfur battery when the locust bean gum is used as the binder in example 1 under the same conditions.
Comparative example 2
The method comprises the following steps of (1) preparing a sulfur-pyrolytic carbon cathode material (mass fraction of sulfur is 47.3%), acetylene black, polyvinylidene fluoride (N-methylpyrrolidone is used as a solvent) according to a mass ratio of 8: 1: 1, fully and uniformly mixing the mixture, coating the mixture on a copper current collector, drying the mixture in a drying oven at 70 ℃ to prepare a pole piece, tabletting the obtained product under the pressure of 1 MPa, carrying out vacuum drying at 80 ℃ for 8 hours, transferring the obtained product into an argon glove box, taking metal magnesium as a negative electrode, adding 0.2mol/L bis (diisopropylamino) magnesium- (magnesium chloride) 2-aluminum trichloride and 1.0mol/L lithium chloride/tetrahydrofuran electrolyte, and assembling the magnesium-sulfur battery. And (4) carrying out constant-current charge and discharge performance test on a battery test system.
As shown in fig. 4, a relationship diagram of the discharge capacity and the cycle number of the magnesium-sulfur battery when the sulfur-pyrolytic polyacrylonitrile is used as the positive electrode material and the polyvinylidene fluoride is used as the binder shows that the first discharge capacity of the battery is 920.5mAh/g, the second discharge capacity is 424.3mAh/g, the cycle 50 discharge capacity is 188.1mAh/g, the discharge capacity retention rate is 44.3%, which is far lower than the cycle stability of the magnesium-sulfur battery when the polyacrylic acid is used as the binder in example 2 under the same condition.
The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.
Claims (6)
1. An application method of a water-based binder in a magnesium-sulfur battery is characterized in that the binder is locust bean gum, and the application method comprises the following steps:
step 1, uniformly mixing the aqueous solution of the binder, a sulfur positive electrode material and a carbon conductive agent, and coating the mixture on a current collector;
step 2, drying the current collector in an oven at 50-100 ℃ to manufacture a pole piece, tabletting under the pressure of 0.2-2.5 MPa, drying in vacuum at 50-130 ℃ for 3-24 hours, and then transferring into an argon glove box;
step 3, taking magnesium metal as a negative electrode, adding electrolyte, and assembling the magnesium-sulfur battery;
the sulfur positive electrode material in the step 1 contains carbon, the mass content of the carbon is more than 0 and less than or equal to 65%, and the carbon is at least one of microporous carbon, mesoporous carbon, macroporous carbon and pyrolytic carbon;
in the step 1, the current collector is any one of copper, aluminum or nickel;
the electrolyte in the step 3 contains ether solution of any one of phenylmagnesium chloride-aluminum trichloride or bis (diisopropylamino) magnesium trichloride;
in the phenylmagnesium chloride-aluminum trichloride, the molar ratio of phenylmagnesium chloride to aluminum trichloride is 3-0.1; in the bis (diisopropylamino) magnesium-aluminum trichloride, the molar ratio of bis (diisopropylamino) magnesium to aluminum trichloride is 3-0.1;
the electrolyte further comprises magnesium chloride;
the molar ratio of any one of phenylmagnesium chloride or bis (diisopropylamino) magnesium to magnesium chloride is 5-0.1.
2. The method for applying the aqueous binder to the magnesium-sulfur battery according to claim 1, wherein the mass ratio of the binder to the sulfur positive electrode material to the carbon conductive agent in step 1 is 6 to 9: 0.5-2: 0.4 to 2.5.
3. The method for using an aqueous binder in a magnesium-sulfur battery according to claim 1, wherein the carbon conductive agent is acetylene black.
4. The method of using an aqueous binder for a magnesium-sulfur battery according to claim 1, wherein the concentration of magnesium ions in the electrolyte is 0.1 to 2.0 mol/L.
5. The method for using an aqueous binder in a magnesium-sulfur battery according to claim 1, wherein the ether is at least one of tetrahydrofuran, 2-methyltetrahydrofuran, 1, 3-dioxolane, diethyl ether, ethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether.
6. The method of using the aqueous binder in a magnesium-sulfur battery according to claim 1, wherein the electrolyte in step 3 further comprises a lithium salt, the lithium salt is at least one of lithium trifluoromethanesulfonate, lithium chloride, lithium fluoride, lithium bromide, lithium nitrate and lithium borohydride, and the concentration of the lithium salt is 0.01 to 2.0 mol/L.
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Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106384844A (en) * | 2016-07-27 | 2017-02-08 | 中国科学院苏州纳米技术与纳米仿生研究所 | Non-nucleophilic dual-salt-system electrolyte for magnesium cell, and preparation method and application thereof |
| CN106531964A (en) * | 2016-10-21 | 2017-03-22 | 上海交通大学 | An aqueous adhesive used for a sulfur cathode and applications thereof |
| CN106898750A (en) * | 2017-03-28 | 2017-06-27 | 苏州大学 | Metal sulphur battery based on sulfur-rich transient metal sulfide and preparation method thereof |
| CN107240679A (en) * | 2016-03-28 | 2017-10-10 | 国家纳米科学中心 | Nitrogen-doped carbon conductive nano network/sulphur composite, preparation method and purposes |
| CN108400340A (en) * | 2018-04-03 | 2018-08-14 | 中国科学院宁波材料技术与工程研究所 | A kind of lithium ion cell positive, preparation method and lithium ion battery |
| CN108493452A (en) * | 2018-03-13 | 2018-09-04 | 陕西科技大学 | It is a kind of to inhibit the aqueous binders of pole piece material expansion and lithium ion battery negative material and preparation method based on it |
| CN109244544A (en) * | 2018-11-19 | 2019-01-18 | 哈尔滨工业大学 | The preparation method and applications of the magnesium sulphur battery electrolyte of the additive containing lithium ion |
| CN109671936A (en) * | 2018-12-19 | 2019-04-23 | 深圳先进技术研究院 | Containing tin negative pole material, cathode and preparation method thereof and negative electrode slurry, secondary cell and electrical equipment |
| CN109713310A (en) * | 2018-12-05 | 2019-05-03 | 上海空间电源研究所 | A kind of lightweight flexibility sulfur electrode and its preparation method and application |
| CN110265712A (en) * | 2019-06-24 | 2019-09-20 | 清华大学 | Magnesium battery electrolyte, preparation method and magnesium cell |
| CN110416618A (en) * | 2019-07-22 | 2019-11-05 | 杭州怡莱珂科技有限公司 | A kind of aluminium ion electrolyte solution and magnesium ion electrolyte solution and battery |
| CN110459742A (en) * | 2019-07-22 | 2019-11-15 | 杭州怡莱珂科技有限公司 | Compound and preparation method thereof and electrode and battery between a kind of carbon-sulfur molecule |
| US10593932B2 (en) * | 2016-09-20 | 2020-03-17 | Global Graphene Group, Inc. | Process for metal-sulfur battery cathode containing humic acid-derived conductive foam |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101587951A (en) * | 2008-05-23 | 2009-11-25 | 中国人民解放军63971部队 | Novel carbon-sulfur compound for lithium-sulfur battery |
| CN101728538A (en) * | 2009-11-26 | 2010-06-09 | 上海大学 | Ordered nanostructure sulphur/mesoporous carbon composite material for anode of lithium ion battery |
| US8361661B2 (en) * | 2011-03-08 | 2013-01-29 | Pellion Technologies Inc. | Rechargeable magnesium ion cell components and assembly |
| CN103050669B (en) * | 2011-10-17 | 2015-04-08 | 中国科学院大连化学物理研究所 | Carbon-sulphur composite used for cathode material of lithium sulphur battery as well as preparation method and application thereof |
| CN102569730A (en) * | 2012-01-31 | 2012-07-11 | 中南大学 | Preparation method for positive plate of lithium-sulfur battery |
| JP2014175246A (en) * | 2013-03-12 | 2014-09-22 | Sony Corp | Secondary battery, method for manufacturing secondary battery, positive electrode for secondary battery, method for manufacturing positive electrode for secondary battery, battery pack, electronic apparatus and electric vehicle |
| JP6399921B2 (en) * | 2014-12-22 | 2018-10-03 | 三星エスディアイ株式会社Samsung SDI Co., Ltd. | Non-aqueous electrolyte secondary battery electrode winding element, non-aqueous electrolyte secondary battery using the same, and non-aqueous electrolyte secondary battery electrode winding element manufacturing method |
| CN105470518A (en) * | 2015-11-24 | 2016-04-06 | 青岛能迅新能源科技有限公司 | Lithium sulfur battery sulfur cathode slurry and preparation method thereof, preparation method of lithium sulfur battery |
| CN106916173B (en) * | 2015-12-28 | 2019-03-08 | 中国科学院苏州纳米技术与纳米仿生研究所 | Monokaryon magnesium cation salt dissolving, preparation method and application |
| CN110600721A (en) * | 2019-09-21 | 2019-12-20 | 盐城增材科技有限公司 | Polyaniline modified sodium polyacrylate lithium-sulfur battery positive electrode material |
-
2020
- 2020-06-22 CN CN202010574177.8A patent/CN111769282B/en not_active Expired - Fee Related
Patent Citations (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107240679A (en) * | 2016-03-28 | 2017-10-10 | 国家纳米科学中心 | Nitrogen-doped carbon conductive nano network/sulphur composite, preparation method and purposes |
| CN106384844A (en) * | 2016-07-27 | 2017-02-08 | 中国科学院苏州纳米技术与纳米仿生研究所 | Non-nucleophilic dual-salt-system electrolyte for magnesium cell, and preparation method and application thereof |
| US10593932B2 (en) * | 2016-09-20 | 2020-03-17 | Global Graphene Group, Inc. | Process for metal-sulfur battery cathode containing humic acid-derived conductive foam |
| CN106531964A (en) * | 2016-10-21 | 2017-03-22 | 上海交通大学 | An aqueous adhesive used for a sulfur cathode and applications thereof |
| CN106898750A (en) * | 2017-03-28 | 2017-06-27 | 苏州大学 | Metal sulphur battery based on sulfur-rich transient metal sulfide and preparation method thereof |
| CN108493452A (en) * | 2018-03-13 | 2018-09-04 | 陕西科技大学 | It is a kind of to inhibit the aqueous binders of pole piece material expansion and lithium ion battery negative material and preparation method based on it |
| CN108400340A (en) * | 2018-04-03 | 2018-08-14 | 中国科学院宁波材料技术与工程研究所 | A kind of lithium ion cell positive, preparation method and lithium ion battery |
| CN109244544A (en) * | 2018-11-19 | 2019-01-18 | 哈尔滨工业大学 | The preparation method and applications of the magnesium sulphur battery electrolyte of the additive containing lithium ion |
| CN109713310A (en) * | 2018-12-05 | 2019-05-03 | 上海空间电源研究所 | A kind of lightweight flexibility sulfur electrode and its preparation method and application |
| CN109671936A (en) * | 2018-12-19 | 2019-04-23 | 深圳先进技术研究院 | Containing tin negative pole material, cathode and preparation method thereof and negative electrode slurry, secondary cell and electrical equipment |
| CN110265712A (en) * | 2019-06-24 | 2019-09-20 | 清华大学 | Magnesium battery electrolyte, preparation method and magnesium cell |
| CN110416618A (en) * | 2019-07-22 | 2019-11-05 | 杭州怡莱珂科技有限公司 | A kind of aluminium ion electrolyte solution and magnesium ion electrolyte solution and battery |
| CN110459742A (en) * | 2019-07-22 | 2019-11-15 | 杭州怡莱珂科技有限公司 | Compound and preparation method thereof and electrode and battery between a kind of carbon-sulfur molecule |
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