CN114976002A - Adhesive, preparation method thereof, lithium-sulfur battery positive electrode and lithium-sulfur battery - Google Patents
Adhesive, preparation method thereof, lithium-sulfur battery positive electrode and lithium-sulfur battery Download PDFInfo
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- 239000000853 adhesive Substances 0.000 title claims abstract description 91
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 90
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229920001983 poloxamer Polymers 0.000 claims abstract description 107
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000011230 binding agent Substances 0.000 claims abstract description 45
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 27
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 24
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 21
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims abstract description 17
- 108010010803 Gelatin Proteins 0.000 claims abstract description 16
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- 235000011852 gelatine desserts Nutrition 0.000 claims abstract description 16
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- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims abstract description 14
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims abstract description 14
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006116 polymerization reaction Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 18
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 15
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- 239000011149 active material Substances 0.000 claims description 12
- 238000004132 cross linking Methods 0.000 claims description 11
- 238000006482 condensation reaction Methods 0.000 claims description 10
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 claims description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
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- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical compound CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 6
- 239000006258 conductive agent Substances 0.000 claims description 6
- -1 polyoxyethylene Polymers 0.000 claims description 6
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims description 5
- 229940014800 succinic anhydride Drugs 0.000 claims description 5
- 229920000428 triblock copolymer Polymers 0.000 claims description 4
- 229920002023 Pluronic® F 87 Polymers 0.000 claims description 3
- HQPMKSGTIOYHJT-UHFFFAOYSA-N ethane-1,2-diol;propane-1,2-diol Chemical compound OCCO.CC(O)CO HQPMKSGTIOYHJT-UHFFFAOYSA-N 0.000 claims description 3
- 229920001993 poloxamer 188 Polymers 0.000 claims description 3
- 229920001992 poloxamer 407 Polymers 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 21
- 229910052717 sulfur Inorganic materials 0.000 abstract description 18
- 239000011593 sulfur Substances 0.000 abstract description 18
- 229920001021 polysulfide Polymers 0.000 abstract description 9
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- 230000004048 modification Effects 0.000 abstract description 8
- 238000012986 modification Methods 0.000 abstract description 8
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical group CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 4
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- 230000000052 comparative effect Effects 0.000 description 4
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
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- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 229920000463 Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) Polymers 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
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- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 description 2
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- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
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- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 1
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- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
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- AEXDMFVPDVVSQJ-UHFFFAOYSA-N trifluoro(trifluoromethylsulfonyl)methane Chemical group FC(F)(F)S(=O)(=O)C(F)(F)F AEXDMFVPDVVSQJ-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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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
- H01M4/622—Binders being polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- 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
- H01M4/62—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
- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application discloses a binder, a preparation method thereof, a lithium-sulfur battery positive electrode and a lithium-sulfur battery, wherein the binder comprises a pluronic and a water system binder, the molar ratio of the pluronic to the water system binder is 1: 1.5-3, and the water system binder comprises one or more of polyacrylic acid, polyethyleneimine, gelatin, cyclodextrin and carboxymethyl cellulose. The preparation method comprises the step of directly polymerizing the pluronic and the water-based adhesive or the step of condensing the pluronic and the water-based adhesive after the pluronic is subjected to end group modification. The adhesive provided by the invention can greatly improve the mechanical adhesive force of the adhesive and can effectively inhibit the diffusion and transfer of polysulfide, thereby improving the utilization rate of active sulfur and improving the cycle life and rate capability of a lithium-sulfur battery.
Description
Technical Field
The application relates to the technical field of lithium-sulfur batteries, in particular to a binder, a preparation method of the binder, a lithium-sulfur battery positive electrode and a lithium-sulfur battery.
Background
Since the lithium ion battery has been commercialized in the 90 s of the 20 th century, communication and transportation modes of people have been innovated, and development of camcorders, mobile phones, notebook computers, and recently electric vehicles has been promoted. But the mass energy density and power of the energy storage device still cannot meet the future requirement of people for energy storage. As the actual energy density of lithium ion batteries gradually approaches the theoretical attainable limit value, it is imperative to research a novel electrochemical energy storage system with energy density higher than that of lithium ion batteries, and among many energy storage systems replacing lithium ion batteries, lithium sulfur batteries are the next generation battery system which is the most practical and promising at present.
Generally, a typical electrode is composed of a current collector, an active material, a conductive agent, and a binder. Although the binder is present in a very small fraction (typically 10% or even less) of the electrode, it is not replaceable. The polymeric binder, which is generally non-conductive and non-electrochemically active, essentially serves to bind the active material and the conductive agent together and then to secure them to the current collector, maintaining electronic contact between the electrode active material and the conductive agent and between the active material and the current collector, stabilizing the electrode structure.
Currently, in the preparation of sulfur positive electrodes, the binder is usually dissolved in an organic solvent, polymethylpyrrolidone (NMP). NMP is expensive, toxic NMP also easily causes environmental problems, and its low flash point and flammability cause safety problems that are not negligible. In addition, the high boiling point of NMP results in the need to process and dry the pole pieces, often at higher temperatures, which is prone to loss of active material.
Disclosure of Invention
The application provides a binder, a preparation method thereof, a lithium-sulfur battery positive electrode and a lithium-sulfur battery, aiming at solving the safety problem caused by an organic solvent and the problem of loss of an active material of the lithium-sulfur battery.
In one aspect, an embodiment of the application provides an adhesive, including pluronic and a water-based adhesive, where a molar ratio of the pluronic to the water-based adhesive is 1: 1.5-3, where the water-based adhesive includes one or more of polyacrylic acid, polyethyleneimine, gelatin, cyclodextrin, and carboxymethyl cellulose.
Optionally, the pluronic is a triblock copolymer with polyoxyethylene at both ends and polyoxypropylene in the middle.
Optionally, the pluronic includes one or more of pluronic L44, pluronic F68, pluronic F87, pluronic F108, and pluronic F127.
In another aspect, an embodiment of the present application provides a method for preparing an adhesive, including the steps of:
the method comprises the following steps of (1) contacting pluronic with a water-based adhesive so as to enable the pluronic and the water-based adhesive to carry out polymerization reaction, and obtaining the adhesive;
or contacting the modified pluronic with a water-based adhesive to perform condensation reaction on the modified pluronic and the water-based adhesive to obtain the adhesive, wherein the modified pluronic is pluronic with a carboxyl group at the tail end, and the water-based adhesive comprises one or more of polyacrylic acid, polyethyleneimine, gelatin, cyclodextrin and carboxymethyl cellulose.
Optionally, the contacting the pluronic with the water-based binder to cause the pluronic and the water-based binder to undergo a polymerization reaction includes:
contacting 1-ethyl- (3-dimethylaminopropyl) carbodiimide with the polyacrylic acid to activate carboxyl groups of the polyacrylic acid to obtain an activated polyacrylic acid;
and contacting the pluronic with the activated polyacrylic acid so as to enable the pluronic and the activated polyacrylic acid to carry out cross-linking polymerization reaction.
Optionally, the contacting the pluronic with the water-based binder to cause the pluronic and the water-based binder to undergo a polymerization reaction includes:
and (3) contacting pluronic with the polyethyleneimine so as to perform cross-linking polymerization reaction on the pluronic and the polyethyleneimine.
Optionally, the contacting the modified pluronic with a water-based binder to perform a condensation reaction between the modified pluronic and the water-based binder includes:
contacting the modified pluronic with gelatin, cyclodextrin or carboxymethyl cellulose to cause a condensation reaction of the modified pluronic with gelatin, cyclodextrin or carboxymethyl cellulose.
Optionally, the preparation method of the modified pluronic comprises the following steps:
contacting pluronic with succinic anhydride, and a catalyst such that the end of the pluronic contains a carboxyl group.
In another aspect, embodiments of the present disclosure provide a positive electrode for a lithium-sulfur battery, including a current collector, an active material, a conductive agent, and the above binder or the binder prepared by the above method.
In still another aspect, embodiments of the present application provide a lithium sulfur battery including a lithium sulfur battery negative electrode, a separator, an electrolyte, and the lithium sulfur battery positive electrode.
Compared with the prior art, the invention has the following advantages and prominent effects:
the pluronic has reverse reversible thermal gelation property, the special low-temperature swelling property can greatly increase the electrolyte intake of the sulfur anode, promote the contact of active sulfur ligands and lithium ions in the electrolyte, the swelling property is reduced at room temperature or above, the porosity of the sulfur anode can be well maintained, the internal resistance of the electrode can be effectively reduced, and the electrochemical reaction kinetics is improved.
The aqueous binder can reduce the use of organic solvents and effectively eliminate the adverse effects of the organic solvents. In addition, there are some organic components of such binders that are insoluble in the electrolyte. Insolubility in organic electrolytes can greatly improve the stability of the electrode during cycling. On the other hand, water-soluble polymer binders generally have abundant surface polar functional groups, such as carboxyl, hydroxyl, amino, etc. The presence of these polar groups promotes the interaction between the binder and the metal current collector, the binder and the active material, and the binder and the polysulfide, thereby improving the mechanical adhesion of the binder and effectively inhibiting the diffusion and migration of the polysulfide.
The adhesive provided by the invention can effectively eliminate adverse effects generated by organic solvents, achieves the purposes of safety and environmental friendliness, and does not cause loss to active materials of lithium-sulfur batteries.
The adhesive is used for the adhesive of the sulfur anode material of the lithium-sulfur battery, so that the mechanical adhesive force of the adhesive can be greatly improved, and the diffusion and transfer of polysulfide can be effectively inhibited, thereby improving the utilization rate of active sulfur, and improving the cycle life and the rate capability of the battery.
Drawings
Features, advantages and technical effects of exemplary embodiments of the present application will be described below with reference to the accompanying drawings.
FIG. 1 is a reaction scheme for the polymerization of Pluronic and polyacrylic acids herein;
FIG. 2 is a reaction scheme for the polymerization of pluronic polyethyleneimine in the present application;
FIG. 3 is a reaction scheme for the modification of Pluronic (end-group-modified carboxylation) in the present application.
Detailed Description
In order to make the objects, technical solutions and advantageous technical effects of the present invention more clear, the present invention is further described in detail with reference to the following embodiments. It should be understood that the embodiments described in this specification are only for the purpose of explaining the present invention and are not intended to limit the present invention.
For the sake of brevity, only some numerical ranges are explicitly disclosed herein. However, any lower limit may be combined with any upper limit to form ranges not explicitly recited; and any lower limit may be combined with any other lower limit to form a range not explicitly recited, and similarly any upper limit may be combined with any other upper limit to form a range not explicitly recited. Also, although not explicitly recited, each point or individual value between endpoints of a range is encompassed within the range. Thus, each point or individual value can form a range not explicitly recited as its own lower or upper limit in combination with any other point or individual value or in combination with other lower or upper limits.
In the description herein, it is to be noted that, unless otherwise specified, "above" and "below" are inclusive, and "a plurality" of "one or more" means two or more.
The above summary of the present invention is not intended to describe each disclosed embodiment or every implementation of the present invention. The following description more particularly exemplifies illustrative embodiments. At various points throughout this application, guidance is provided through a list of embodiments that can be used in various combinations. In various embodiments, the lists are provided as representative groups and should not be construed as exhaustive.
In the lithium-sulfur battery, due to the density difference between elemental sulfur and the discharge product, the sulfur positive electrode undergoes huge volume expansion and contraction (80%) during the cycling process, which requires a good mechanical modulus for the binder to buffer the volume change during the cycling process and maintain the stability and integrity of the positive electrode structure. In addition, the ideal binder for lithium-sulfur batteries should have the following characteristics: high ionic/electronic conductivity; the ability to inhibit the shuttle effect; the ability to enhance redox kinetics.
Adhesive agent
Embodiments of the first aspect of the present disclosure provide an adhesive, including pluronic and a water-based adhesive, where a molar ratio of the pluronic to the water-based adhesive is 1: 1.5-3, where the water-based adhesive includes one or more of polyacrylic acid, polyethyleneimine, gelatin, cyclodextrin, and carboxymethyl cellulose.
In the embodiment of the application, propylene glycol is taken as an initiator, and the propylene oxide and ethylene oxide are sequentially subjected to anion ring-opening polymerization reaction to obtain a triblock copolymer (PEO-PPO-PEO) with polyethylene oxide (PEO) at two ends and polypropylene oxide (PPO) in the middle, and one or more of five block copolymers including liquid L44, solid F68, solid F87, solid F108, solid F127 and the like at normal temperature are obtained by regulating the proportion of ethylene oxide and propylene oxide. Are all commercially available.
According to the embodiment of the application, the pluronic has reverse reversible thermal gelation properties, the specific low-temperature swelling property can greatly increase the electrolyte intake of the sulfur anode, promote the contact of active sulfur ligands and lithium ions in the electrolyte, the swelling property is reduced at room temperature or above, the porosity of the sulfur anode can be well maintained, the internal resistance of the electrode can be effectively reduced, and the electrochemical reaction kinetics is improved.
The water-based adhesive belongs to a water-based solvent, and compared with an organic solvent, the water-based solvent has the characteristics of low price, safety, environmental friendliness and the like. Therefore, water-based adhesives have received increasing attention.
According to the embodiment of the present application, on the one hand, the water-based binder can reduce the use of the organic solvent, and effectively eliminate the adverse effect of the organic solvent. In addition, there are some organic components of such binders that are insoluble in the electrolyte. Insolubility in organic electrolytes can greatly improve the stability of the electrode during cycling. On the other hand, water-soluble polymer binders generally have abundant surface polar functional groups, such as carboxyl, hydroxyl, amino, etc. The presence of these polar groups promotes the interaction between the binder and the metal current collector, the binder and the active material, and the binder and the polysulfide, thereby improving the mechanical adhesion of the binder and effectively inhibiting the diffusion and migration of the polysulfide.
In order to ensure that the sufficient polymerization or condensation reaction occurs after the pluronic is contacted with the water-based adhesive, the molar ratio of the pluronic to the water-based adhesive is 1: 1.5-3. For example, the molar ratio of pluronic to the aqueous binder is 1:1.5, 1:2, 1:2.5, or 1:3, etc. The molar ratio of pluronic to the water-based binder may be a combination of any of the above numerical ranges.
The adhesive is used as the adhesive of the sulfur anode material of the lithium sulfur battery, so that the mechanical adhesive force of the adhesive can be greatly improved, and the diffusion and transfer of polysulfide can be effectively inhibited, thereby improving the utilization rate of active sulfur, and improving the cycle life and the rate capability of the battery. The adhesive provided by the invention can also effectively eliminate adverse effects generated by organic solvents, achieves the purposes of safety and environmental friendliness, and does not cause loss to active materials of lithium-sulfur batteries.
The binder provided by the embodiment of the application can be used for a positive electrode of a lithium-sulfur battery.
In the examples of the present application, the pluronic is a triblock copolymer (PEO-PPO-PEO) having polyethylene oxide (PEO) at both ends and polypropylene oxide (PPO) in the middle.
In embodiments of the present application, the pluronic includes one or more of pluronic L44, pluronic F68, pluronic F87, pluronic F108, and pluronic F127. Having the general formula HO (C) 2 H 4 O) a (C 3 H 6 O) b (C 2 H 4 O) c H. a is polyoxyethylene at two ends, and b is middle polyoxypropylene. Table 1 shows some physicochemical properties of pluronic.
TABLE 1 physical Properties of Pluronic
Preparation method of adhesive
Embodiments of the second aspect of the present application provide a method for preparing an adhesive, including the following steps:
the method comprises the following steps of (1) contacting pluronic with a water-based adhesive so as to enable the pluronic and the water-based adhesive to carry out polymerization reaction, and obtaining the adhesive;
or contacting the modified pluronic with a water-based adhesive to perform a condensation reaction between the modified pluronic and the water-based adhesive to obtain the adhesive, wherein the modified pluronic is the pluronic with a terminal carboxyl group, and the water-based adhesive comprises one or more of polyacrylic acid, polyethyleneimine, gelatin, cyclodextrin and carboxymethyl cellulose.
In the embodiment of the application, the adhesive is prepared by directly polymerizing pluronic and a water-based adhesive or condensing pluronic after end group modification and the water-based adhesive.
The preparation method of the adhesive provided by the application can be used for preparing the adhesive provided by the embodiment of the first aspect. The method has simple steps and low cost, and the prepared binder system is stable.
In an embodiment of the present application, the contacting the pluronic with the water-based adhesive to cause the pluronic and the water-based adhesive to undergo a polymerization reaction includes:
contacting 1-ethyl- (3-dimethylaminopropyl) carbodiimide with the polyacrylic acid to activate carboxyl groups of the polyacrylic acid to obtain an activated polyacrylic acid;
and contacting the pluronic with the activated polyacrylic acid so as to enable the pluronic and the activated polyacrylic acid to carry out cross-linking polymerization reaction.
In an embodiment of the present application, the contacting the pluronic with the water-based adhesive to cause the pluronic and the water-based adhesive to undergo a polymerization reaction includes:
and (2) contacting pluronic with the polyethyleneimine, so that the pluronic and the polyethyleneimine are subjected to crosslinking polymerization reaction.
In some embodiments, the adhesive of the present invention is prepared by direct polymerization of pluronic and water-based adhesive or by end group modification of pluronic, and then condensation with water-based adhesive, and comprises:
polymerization with polyacrylic acid (PAA) polyacrylic acid was first carboxyl-activated with 1-ethyl- (3-dimethylaminopropyl) carbodiimide to crosslink with Pluronic. The reaction formula is shown in figure 1.
And the cross-linking polymerization is carried out with Polyethyleneimine (PEI), the polyethyleneimine has higher reactivity, and the open-loop polymerization reaction is carried out with the terminal epoxy group of the pluronic, so that the polyethyleneimine and the pluronic are subjected to cross-linking polymerization. The reaction formula is shown in figure 2.
In an embodiment of the present application, the contacting the modified pluronic with a water-based binder to perform a condensation reaction between the modified pluronic and the water-based binder includes:
contacting the modified pluronic with gelatin, cyclodextrin or carboxymethyl cellulose to cause a condensation reaction of the modified pluronic with gelatin, cyclodextrin or carboxymethyl cellulose.
In an embodiment of the present application, the preparation method of the modified pluronic comprises the following steps:
contacting pluronic with succinic anhydride and a catalyst such that the end of the pluronic contains a carboxyl group.
According to the examples of the present application, Gelatin (GEL), cyclodextrin (β -CD), and carboxymethylcellulose (CMC) are subjected to condensation polymerization by performing terminal group modification carboxylation on pluronic because they have a large number of hydroxyl groups. The formula of the carboxylation reaction is shown in figure 3.
In some embodiments, the catalyst is DMAP/TEA.
Positive electrode of lithium-sulfur battery
Embodiments of the third aspect of the present application provide a positive electrode of a lithium-sulfur battery, including a current collector, an active material, a conductive agent, and a binder as described in embodiments of the first aspect or prepared by the method as provided in embodiments of the second aspect.
The adhesive provided by the embodiment of the first aspect of the application or the adhesive prepared by the method provided by the embodiment of the second aspect of the application can greatly improve the mechanical adhesion of the adhesive and can effectively inhibit the diffusion and transfer of polysulfide, so that the utilization rate of active sulfur is improved.
Lithium-sulfur battery
Embodiments of a fourth aspect of the present application provide a lithium sulfur battery, a lithium sulfur battery negative electrode, a separator, an electrolyte, and a lithium sulfur battery positive electrode provided by embodiments of the third aspect.
In embodiments of the present application, the lithium sulfur battery negative electrode comprises a commercial metallic lithium flake or nanostructured metallic lithium; the electrolyte system adopts 1, 3-dioxolane/ethylene glycol dimethyl ether with the volume ratio of 1 (0.1-10); lithium salt in the electrolyte adopts bis (trifluoromethyl) sulfonyl imide lithium, and the concentration of the lithium salt is 1.0-3.0 mol/L.
The embodiment of this application third aspect provides a binder in lithium sulfur battery positive pole can improve the mechanical adhesion of binder greatly and can effectively restrain polysulfide's diffusion and transfer to promote active sulfur's utilization ratio, promote lithium sulfur battery's cycle life and multiplying power performance, hopefully use in the rechargeable battery of portable electronic product, electric tool and electric automobile etc..
Examples
The present disclosure is more particularly described in the following examples that are intended as illustrative only, since various modifications and changes within the scope of the present disclosure will be apparent to those skilled in the art. Unless otherwise indicated, all parts, percentages, and ratios reported in the following examples are on a weight basis, and all reagents used in the examples are commercially available or synthesized according to conventional methods and can be used directly without further treatment, and the equipment used in the examples is commercially available.
Example 1
The embodiment provides an F127-PAA composite adhesive, and a preparation method thereof includes the following steps:
weighing PAA, dissolving in deionized water, stirring to dissolve completely, adding 1-ethyl- (3-dimethylaminopropyl) carbodiimide (EDC), adjusting pH to 7 with 1M sodium hydroxide, stirring at room temperature in a dark place for 24h, adding purified F127, and continuously stirring in a dark place for 48 h. Dialyzing the reaction solution in 1% NaCl solution for 3 days, dialyzing with distilled water for 3 days, and freeze drying.
Example 2
The embodiment provides an F127-PEI composite adhesive, and the preparation method comprises the following steps:
weighing PEI, dissolving in a sodium hydroxide solution with the pH value of 11, adding F127, reacting for a certain time at the temperature of 70 ℃ under the protection of nitrogen, washing a product to be neutral by water, and drying for 24 hours in vacuum to obtain the F127-PEI.
Example 3
The embodiment provides an F127-GEL composite adhesive, and a preparation method thereof comprises the following steps:
the end modification of the pluronic is carried out by reacting hydroxyl at the end of the pluronic with succinic anhydride, the pluronic, the succinic anhydride and DMAP/TEA are dissolved in anhydrous 1, 4-dioxane, stirred overnight, heated and dried in vacuum to remove the solvent, then poured into excessive cold ether to obtain precipitate, filtered, repeatedly precipitated and filtered twice, and freeze-dried for 48 hours to obtain the pluronic with carboxyl at the end. Then carrying out esterification crosslinking reaction with gelatin under the action of a p-toluenesulfonic acid catalyst to obtain F127-GEL.
Example 4
The present embodiment provides an F127- β -CD composite adhesive, and the preparation method thereof includes the following steps:
the preparation of the pluronic containing carboxyl at the terminal is the same as that in the example 3, and then the pluronic and the beta-CD are subjected to esterification crosslinking reaction under the action of a p-toluenesulfonic acid catalyst to obtain F127-beta-CD.
Example 5
The embodiment provides an F127-CMC composite adhesive, and the preparation method comprises the following steps:
the preparation of the pluronic with the carboxyl at the end is the same as that in the example 3, and then the pluronic and the CMC are subjected to esterification crosslinking reaction under the action of a p-toluenesulfonic acid catalyst to obtain the F127-CMC.
Comparative example
Comparative example 1
Preparing sulfur anode slurry, namely fully mixing carbon powder and sulfur powder under a dry solid condition, then carrying out hot melting at a certain temperature to inject the sulfur powder into a porous structure of the carbon powder, and then cooling to obtain carbon-sulfur composite powder; the dispersion solutions of examples 1 to 5 and comparative example 1 and the carbon-sulfur composite powder were thoroughly stirred to obtain a sulfur positive electrode slurry. Adopting a metal lithium cathode, wherein the dosage ratio of electrolyte DOL/DME is 1:1, 1mol/L LiTFSI, and the novel lithium-sulfur battery is obtained through the steps of packaging, standing, formation, aging, secondary packaging, pre-circulation and the like.
In the embodiment of the application, the lithium-sulfur battery prepared by selecting a suitable positive electrode sulfur composite system, negative electrode metal lithium, lithium salt and organic solvent and matching with the method of the first aspect of the application has excellent shuttle effect inhibition capability, the swelling capacity at low temperature can effectively improve the characteristics of an electrode interface, the low swelling characteristic at room temperature and above can well maintain the porosity of the sulfur positive electrode, the prepared soft package lithium-sulfur battery can be fully soaked by electrolyte by adopting a low-temperature formation process, can reach higher initial discharge specific capacity and maintain stable charge-discharge cycle performance, and the result is shown in table 2.
TABLE 2 test results of examples 1 to 5 and comparative example 1
While the invention has been described with reference to specific embodiments, the scope of the invention is not limited thereto, and those skilled in the art can easily conceive various equivalent modifications or substitutions within the technical scope of the invention. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.
Claims (10)
1. The adhesive is characterized by comprising pluronic and a water-based adhesive, wherein the molar ratio of the pluronic to the water-based adhesive is 1: 1.5-3, and the water-based adhesive comprises one or more of polyacrylic acid, polyethyleneimine, gelatin, cyclodextrin and carboxymethyl cellulose.
2. The adhesive of claim 1 wherein the pluronic is a triblock copolymer having polyoxyethylene at each end and polyoxypropylene in the middle.
3. The adhesive of claim 1, wherein said pluronic comprises one or more of pluronic L44, pluronic F68, pluronic F87, pluronic F108, and pluronic F127.
4. The preparation method of the adhesive is characterized by comprising the following steps:
the method comprises the following steps of (1) contacting pluronic with a water-based adhesive so as to enable the pluronic and the water-based adhesive to carry out polymerization reaction, and obtaining the adhesive;
or contacting the modified pluronic with a water-based adhesive to perform condensation reaction on the modified pluronic and the water-based adhesive to obtain the adhesive, wherein the modified pluronic is pluronic with terminal carboxyl,
wherein the water-based adhesive comprises one or more of polyacrylic acid, polyethyleneimine, gelatin, cyclodextrin and carboxymethyl cellulose.
5. The method for preparing the adhesive according to claim 4, wherein the step of contacting pluronic with a water-based adhesive to perform polymerization reaction of pluronic and the water-based adhesive comprises:
contacting 1-ethyl- (3-dimethylaminopropyl) carbodiimide with the polyacrylic acid to activate carboxyl groups of the polyacrylic acid to obtain an activated polyacrylic acid;
and contacting the pluronic with the activated polyacrylic acid so as to enable the pluronic and the activated polyacrylic acid to carry out cross-linking polymerization reaction.
6. The method for preparing the adhesive according to claim 4, wherein the step of contacting pluronic with a water-based adhesive to perform polymerization reaction of pluronic and the water-based adhesive comprises:
and (2) contacting pluronic with the polyethyleneimine, so that the pluronic and the polyethyleneimine are subjected to crosslinking polymerization reaction.
7. The method for preparing the adhesive according to claim 4, wherein the step of contacting the modified pluronic with the water-based adhesive to perform a condensation reaction between the modified pluronic and the water-based adhesive comprises:
contacting the modified pluronic with gelatin, cyclodextrin or carboxymethyl cellulose to cause a condensation reaction of the modified pluronic with gelatin, cyclodextrin or carboxymethyl cellulose.
8. The preparation method of the adhesive according to any one of claims 4 to 7, wherein the preparation method of the modified pluronic comprises the following steps:
contacting pluronic with succinic anhydride, and a catalyst such that the end of the pluronic contains a carboxyl group.
9. A positive electrode for a lithium-sulfur battery, comprising a current collector, an active material, a conductive agent, and the binder of any one of claims 1 to 3 or the binder prepared by the method of any one of claims 4 to 8.
10. A lithium-sulfur battery comprising a lithium-sulfur battery negative electrode, a separator, an electrolyte, and the lithium-sulfur battery positive electrode of claim 9.
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