CN113363491B - Preparation method of animal glue binder for lithium-sulfur battery cathode - Google Patents
Preparation method of animal glue binder for lithium-sulfur battery cathode Download PDFInfo
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- CN113363491B CN113363491B CN202110650473.6A CN202110650473A CN113363491B CN 113363491 B CN113363491 B CN 113363491B CN 202110650473 A CN202110650473 A CN 202110650473A CN 113363491 B CN113363491 B CN 113363491B
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- sulfur
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- 239000003292 glue Substances 0.000 title claims abstract description 57
- 241001465754 Metazoa Species 0.000 title claims abstract description 50
- 239000011230 binding agent Substances 0.000 title claims abstract description 46
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 21
- 239000011593 sulfur Substances 0.000 claims abstract description 21
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229960001149 dopamine hydrochloride Drugs 0.000 claims abstract description 6
- 239000011149 active material Substances 0.000 claims abstract description 4
- 238000006467 substitution reaction Methods 0.000 claims abstract description 3
- XVOYSCVBGLVSOL-REOHCLBHSA-N L-cysteic acid Chemical compound OC(=O)[C@@H](N)CS(O)(=O)=O XVOYSCVBGLVSOL-REOHCLBHSA-N 0.000 claims abstract 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract 4
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract 4
- 238000007112 amidation reaction Methods 0.000 claims abstract 2
- 150000003943 catecholamines Chemical group 0.000 claims abstract 2
- 239000006182 cathode active material Substances 0.000 claims abstract 2
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- 238000003756 stirring Methods 0.000 claims description 20
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
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- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 4
- LCTONWCANYUPML-UHFFFAOYSA-N Pyruvic acid Chemical compound CC(=O)C(O)=O LCTONWCANYUPML-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
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- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
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- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 239000000174 gluconic acid Substances 0.000 claims description 2
- 235000012208 gluconic acid Nutrition 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
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- 150000007524 organic acids Chemical class 0.000 claims description 2
- 229940107700 pyruvic acid Drugs 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims 2
- 239000003153 chemical reaction reagent Substances 0.000 claims 1
- FBBDOOHMGLLEGJ-UHFFFAOYSA-N methane;hydrochloride Chemical compound C.Cl FBBDOOHMGLLEGJ-UHFFFAOYSA-N 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 21
- 239000010406 cathode material Substances 0.000 abstract description 5
- 239000003013 cathode binding agent Substances 0.000 abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 2
- 229920001328 Polyvinylidene chloride Polymers 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 239000002270 dispersing agent Substances 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
- 239000005033 polyvinylidene chloride Substances 0.000 abstract 1
- 239000002033 PVDF binder Substances 0.000 description 20
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- 229920001021 polysulfide Polymers 0.000 description 8
- 239000005077 polysulfide Substances 0.000 description 8
- 150000008117 polysulfides Polymers 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
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- 238000001179 sorption measurement Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
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- 239000003792 electrolyte Substances 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 241000237536 Mytilus edulis Species 0.000 description 3
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- 239000011888 foil Substances 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 235000020638 mussel Nutrition 0.000 description 3
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- 239000000126 substance Substances 0.000 description 3
- MGBKJKDRMRAZKC-UHFFFAOYSA-N 3-aminobenzene-1,2-diol Chemical group NC1=CC=CC(O)=C1O MGBKJKDRMRAZKC-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 125000002015 acyclic group Chemical group 0.000 description 2
- 229920001222 biopolymer Polymers 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012490 blank solution Substances 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical group OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
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- 235000019322 gelatine Nutrition 0.000 description 2
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- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000002211 ultraviolet spectrum Methods 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 241000589651 Zoogloea Species 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
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- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
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- 239000007772 electrode material Substances 0.000 description 1
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- 230000002349 favourable effect Effects 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
- 229940116298 l- malic acid Drugs 0.000 description 1
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- 238000011056 performance test Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
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- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 230000014233 sulfur utilization Effects 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
-
- 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
-
- 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)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses an animal glue binder for a cathode of a lithium-sulfur battery and a preparation method thereof, wherein the cathode binder of the lithium-sulfur battery is prepared by compounding and modifying animal glue by 3-sulfo-alanine and dopamine hydrochloride. The novel composite binder for preparing the lithium-sulfur battery by using the natural biological polymer animal glue replaces the traditional binder polyvinylidene chloride, the amino and the carboxyl in the animal glue molecule respectively generate amidation reaction with the carboxyl in the 3-sulfo-alanine molecule and the amino in the hydrochloric acid dopamine molecule, and-SO in the 3-sulfo-alanine molecule3The H group can fix the cathode active material through substitution reaction, so that the utilization rate of the sulfur active material is improved; the catechol amine group in dopamine hydrochloride can more firmly protect the structural integrity of the sulfur cathode. The animal glue composite modified binder not only can be used as a binder, but also can be used as a strong dispersing agent of a cathode material, and the binder is simple to prepare and synthesize, has good electrochemical stability and longer cycle life.
Description
Technical Field
The invention belongs to the technical field of lithium-sulfur batteries, and particularly relates to a preparation method of an animal glue binder for a cathode of a lithium-sulfur battery.
Background
The high-performance adhesive has extremely high adhesion capability of an electrode material to a current collector, and the lithium-sulfur battery with high energy density can meet all requirements of energy storage equipment in modern life, such as mobile phones, electric automobiles, chargers and the like. However, the insulation of sulfur and sulfide, the dissolution and shuttling of polysulfide, and the volume fluctuation of sulfur still prevent the general use of the sulfur. Currently, the research focus of lithium batteries is to increase the interaction of insulating sulfur with conductive agents. In particular, in the composition of the sulfur cathode, the inner surface of the sulfur cathode is coated with a binder, by which a connection is established between the conductive material and the active material, which has high adhesion ability and the ability to form a good electrical network between the active material and the conductive carbon, to promote electron transport and diffusion ions of lithium, thereby improving cycle life and sulfur utilization of the lithium-sulfur battery.
Polyvinylidene fluoride (PVDF) has good electrochemical stability, good wettability with electrolyte and acceptable adhesion between electrode laminates and current collectors, and is one of the most widely used binders for sulfur cathodes today. However, PVDF is used by dissolving in a toxic and harmful N-methyl-1-2-pyrrolidone (NMP) solvent, which causes safety problems and serious pollution. Meanwhile, PVDF is very sensitive to humidity, and under a humid condition, the adhesive capacity is rapidly reduced due to water absorption, and the PVDF falls off and loses efficacy. It is therefore important to find other inexpensive, non-toxic and environmentally friendly binders for improving electrochemical performance and reducing the manufacturing cost of the battery. At present, patent CN103682361B discloses a binder for a positive electrode of a lithium-sulfur battery, which has a capacity retention rate of 63% or more after 100 cycles at a current density of 0.2C, but the binder is liable to block during preparation, and the adhesive capacity of the binder is reduced. Patent CN105226288B discloses the use of a binder for lithium-sulfur batteries, which has good cycling performance, and the electrode skeleton does not collapse after 50 cycles, but the energy density of the battery is lower than 110 Wh/kg. Based on bionics, dopamine hydrochloride and L-RG molecules are introduced to react with natural biological high-molecular animal glue to generate a cathode binder which has good adhesion, lithium ion transmission capacity and polysulfide strong chemical adsorption capacity, is beneficial to inhibiting shuttle effect, and realizes the application of marine organisms and natural high-molecular materials in lithium-sulfur batteries.
Disclosure of Invention
The first invention of the present invention is directed to: the binder of the lithium-sulfur battery prepared from the natural biopolymer animal glue is low in cost, simple in synthesis process and basically insoluble in common organic electrolyte solvents, overcomes the defects of high cost, difficult process control, environmental pollution and the like of the existing PVDF, replaces the traditional PVDF binder, and has the potential of large-scale commercial application.
The second invention of the present invention is directed to: the L-RG molecule reacts with the animal glue molecule, and a sulfonic polar group is introduced, so that the animal glue binder has better lithium ion transmission capacity and polysulfide strong chemical adsorption capacity, is favorable for inhibiting shuttle effect, and solves the problems of poor binding performance and weak shuttle effect inhibition capacity of PVDF (polyvinylidene fluoride).
The third invention of the present invention is directed to: based on bionics, the invention introduces catecholamine group which mainly plays a role in bonding in marine high-viscosity biological mussels, so that the marine high-viscosity biological mussels can still retain high bonding strength in a wet electrolyte, and the defects that gelatin is extremely brittle and easy to fall off in a cathode material are overcome.
In order to achieve the purpose, the invention is realized by the following technical scheme: 1) placing BG and water in a three-neck flask, heating in 50 deg.C water bath, mechanically stirring at 100r/min for 30min to obtain yellow bone glue solution; 2) slowly adding 100mL of 1mol/L hydrolytic agent into the yellow bone glue solution in the step 1), and continuously mechanically stirring for 40min at 100r/min in a water bath at 50 ℃ to obtain a bone glue hydrolytic solution; 3) placing the bone glue hydrolysis solution in the step 2) into an oil bath kettle at 70 ℃, slowly adding L-RG powder, mechanically stirring for 5 hours at 150r/min, and filtering while hot to remove incompletely dissolved bone glue gel; 4) 1.2% strength N is introduced2Adding C into the filtrate obtained in the step 3)8H12ClNO2Stirring for 12 hours at 150r/min under the heating of 100 ℃ oil bath to obtain light yellow glue solution; 5) and (3) placing the light yellow glue solution obtained in the step 4) into a rotary evaporator, performing rotary evaporation and concentration at 120r/min for 60min, and then placing into a vacuum drier at the temperature of-30 ℃ to freeze into powder, thus obtaining the animal glue binder for the cathode of the lithium-sulfur battery. The invention relates to a preparation method of a high-efficiency and high-efficiency composite material, which comprises the following raw material components in percentage by weight: 27.8% -38.5% BG, 6.9% -8.2% L-RG, 9.7% -15.4% C8H12ClNO2The balance of water; in the step 2), the hydrolytic agent is one or two of natural organic acids such as tartaric acid, malic acid, citric acid, succinic acid, gluconic acid, citric acid, pyruvic acid and the like.
The invention has the beneficial effects that:
1. the invention provides a binder of a lithium-sulfur battery prepared from natural biopolymer animal glue, which has the advantages of low cost, simple synthesis process and insolubility in common organic electrolyte solvents, overcomes the defects of high cost, difficult process control, environmental pollution and the like of the existing PVDF, thereby replacing the traditional PVDF binder and having the potential of large-scale commercial application;
2. the invention provides a preparation method of an animal glue binder for a lithium-sulfur battery cathode, wherein L-RG molecules react with animal glue molecules, and sulfonate polar groups are introduced, so that the animal glue binder has better lithium ion transmission capability and polysulfide strong chemical adsorption capacity, is beneficial to inhibiting shuttle effect, and overcomes the problems of poor bonding performance, weak shuttle effect inhibition capability and the like of PVDF.
3. The invention provides a preparation method of an animal glue binder for a cathode of a lithium-sulfur battery, which introduces catecholamine groups which mainly play a role in binding in marine high-viscosity biological mussels based on bionics, so that the animal glue can still retain high binding strength in a wet electrolyte, and overcomes the defects that the animal glue is extremely fragile and easy to fall off in a cathode material.
Drawings
Fig. 1 is a diagram illustrating a process for preparing an adhesive binder for a cathode of a lithium sulfur battery.
Fig. 2 is a reaction equation diagram of an animal glue binder for a cathode of a lithium sulfur battery.
Fig. 3 is an infrared spectrum of an animal glue binder for a lithium sulfur battery cathode.
FIG. 4 is a UV spectrum of the cathode binder adsorbing sulfur.
FIG. 5 is a scanning electron microscope image of the cathode consisting of PVDF and composite modified animal glue under different circulation conditions.
Fig. 6 is a graph of rate performance for different sulfur cathodes.
Figure 7 shows the self-discharge rates of different sulfur cathodes.
Fig. 8 is a comparison of electrochemical performance at different sulfur-based electrode 1C rates.
Detailed Description
The technical solution of the present invention will be described clearly and completely with reference to the following embodiments, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention; all other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Preparation of animal glue binder for lithium-sulfur battery cathode
Example 1:
placing 28.0 wt.% BG and 54 wt.% water in a three-neck flask, heating in a water bath at 50 deg.C, mechanically stirring at 100r/min for 30min, and slowly adding 100mL of 1Continuously mechanically stirring the citric acid mol/L at the temperature of 50 ℃ in a water bath for 40min at the speed of 100r/min, taking out the three-neck flask, putting the three-neck flask into an oil bath kettle at the temperature of 70 ℃, slowly adding 7.0 wt.% of L-RG powder, mechanically stirring the mixture for 5h at the speed of 250r/min, and filtering the mixture while the mixture is hot to remove bone glue gel which is not completely dissolved; subsequently, 1.2% N was passed in211.0 wt.% C was added with 100 deg.C oil bath heating8H12ClNO2Stirring for 12h at 400r/min under the heating of 100 ℃ oil bath, pouring out the glue solution into a rotary evaporator, carrying out rotary evaporation and concentration for 60min at 200r/min, and then placing into a vacuum drier at-30 ℃ to freeze into powder, thus obtaining the animal glue binder for the cathode of the lithium-sulfur battery.
Example 2:
placing 35.0 wt.% BG and 47 wt.% water in a three-neck flask, heating in a 50 ℃ water bath, mechanically stirring for 30min at 100r/min, slowly adding 100mL of 1mol/L tartaric acid, continuously mechanically stirring for 40min at 50 ℃ water bath at 100r/min, taking out the three-neck flask, placing in a 70 ℃ oil bath kettle, slowly adding 8.0 wt.% L-RG powder, mechanically stirring for 5h at 250r/min, and filtering to remove incompletely dissolved bone glue gel while hot; subsequently, 1.2% N was passed in210.0 wt.% C was added with 100 deg.C oil bath heating8H12ClNO2Stirring for 12h at 400r/min under the heating of 100 ℃ oil bath, pouring out the glue solution into a rotary evaporator, carrying out rotary evaporation and concentration for 60min at 200r/min, and then placing into a vacuum drier at-30 ℃ to freeze into powder, thus obtaining the animal glue binder for the cathode of the lithium-sulfur battery.
Example 3:
putting 38.0 wt.% BG and 40.1 wt.% water in a three-neck flask, heating in a 50 ℃ water bath, mechanically stirring for 30min at 100r/min, slowly adding 100mL of 1mol/L malic acid, continuously mechanically stirring for 40min at 50 ℃ water bath at 100r/min, taking out the three-neck flask, putting in a 70 ℃ oil bath, slowly adding 7.6 wt.% L-RG powder, mechanically stirring for 5h at 250r/min, and filtering while hot to remove incompletely dissolved bone glue gel; subsequently, 1.2% N was passed in214.3 wt.% C was added with 100 deg.C oil bath heating8H12ClNO2Stirring at 400r/min for 12 hr under 100 deg.C oil bath heating, pouring out the glue solution, rotary evaporating at 200r/min for concentrationAfter 60min of condensation, the mixture is frozen into powder in a vacuum drier at the temperature of minus 30 ℃, and the animal glue binder for the cathode of the lithium-sulfur battery is obtained.
Electrochemical performance test and characterization of animal glue binder for lithium-sulfur battery cathode
The assembled lithium-sulfur battery to which the invention relates is a CR2016 type button cell and a series of electrochemical tests were performed. The specific assembly process is as follows:
sublimed sulphur and acetylene black were dried for 5h at 70 ℃ under vacuum. Preparing a mixture of 63 wt.% sublimed sulfur, 7 wt.% binder and 30 wt.% acetylene black, performing ball milling to obtain slurry, coating the slurry on an Al foil by using a scraper, performing vacuum drying at 70 ℃ for 12 hours, and cutting the coated Al foil into circular electrode plates with the diameter of 12 cm. And in the glove box filled with Ar, the prepared circular electrode slice is taken as a cathode, the Li foil is taken as an anode, and the PP/PE/PP is taken as a diaphragm, so that the button cell is assembled. Meanwhile, the electrolyte used by the battery is a mixed solution of 1.0mol/L lithium bis (trifluoromethyl) sulfonyl imide dissolved in 1, 2-dimethoxyethane/1, 3-dioxolane (the volume ratio is 1: 1).
Fig. 2 is a reaction equation diagram of the binder for the composite modified animal glue cathode, and it can be proved from fig. 2 that the preparation method of the cathode animal glue binder is feasible from the analysis of a chemical reaction mechanism. FIG. 3 is an infrared spectrum of an animal glue binder for a lithium sulfur battery cathode, wherein a is an animal glue and b is a composite modified animal glue; as can be seen from FIG. 3, the modified gelatin molecule has reduced amino group content and increased carbonyl group content, and is 634cm-1And 527cm-1Characteristic absorption peaks of sulfonic acid groups appear. Meanwhile, the curve after composite modification is 1246cm-1A C-O-S stretching vibration peak appears at 1432cm-1The characteristic peak of the catechol group appears, and the curve b proves that the sulfo group in the L-RG molecule and the catechol group in the dopamine hydrochloride are successfully grafted on the animal glue. FIG. 4 is a UV spectrum of the cathode binder adsorbing sulfur. Wherein a is a blank solution of polysulfide, b is a PVDF binder, and c is a composite modified animal glue binder; compared with the blank solution and PVDF curve, the absorption peak of the composite modified animal glue curve isWeakly, indicating that the solution contains lower concentrations of polysulfide due to the stronger adsorption of polysulfide by the composite modified zoogloea compared to PVDF. FIG. 5 is a scanning electron microscope image of the cathode material, wherein a-d are respectively an acyclic composite animal glue cathode, a 50-cycle composite animal glue cathode, an acyclic PVDF cathode, and a 50-cycle PVDF cathode. As can be seen from fig. 5, after 50 cycles, the composite zoon cathode still shows good integrity and sulfur particles are uniformly dispersed on the surface, but the PVDF cathode shows obvious aggregation and partial peeling on the surface, which indicates that the lithium-sulfur battery with the composite zoon binder has better capacity and cycling durability, does not swell in organic electrolyte solvent, and can maintain good conductivity between the cathode material and the current collector.
FIG. 6 is a graph of rate performance of different sulfur cathodes, as can be seen, at 0.1C, the initial specific discharge capacities of the electrodes of examples 1-3 of the composite modified animal glue binder electrode were 1250mAh/g, 1235mAh/g, and 1300mAh/g, respectively, which are much greater than the PVDF electrode; when the current density is recovered to 1C, the specific discharge capacity of the electrode of the composite modified animal glue binder is about 725mAh/g, which shows that the cathode of the composite modified animal glue binder has better capacity recovery rate. Figure 7 shows the self-discharge rates of different sulfur cathodes. It can be seen that as the shelf time increases, the self-discharge rate of the battery increases. However, in the same time, the self-discharge rates of the composite modified animal glue binders of examples 1 to 3 are higher, and the self-discharge rate of the PVDF electrode is lower, which indicates that the composite animal glue binder has stronger adsorption capacity to polysulfide and inhibits the shuttling effect thereof, so that the lithium-sulfur battery can store more electricity. Fig. 8 is a comparison of electrochemical performance at different sulfur-based electrode 1C rates. The table shows that the initial specific discharge capacity of the sulfur cathode of the composite modified animal glue binder of examples 1-3 is above 885m Ah/g, and after 500 cycles, the capacity retention rate is above 53.17%, which indicates that the electrode capacity retention rate of the composite modified animal glue is higher and the cycle stability is better.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (4)
1. The preparation method of the animal glue binder for the cathode of the lithium-sulfur battery is characterized in that the animal glue binder comprises the following raw material components:
27.8% -38.5% of animal glue BG, 6.9% -8.2% of 3-sulfo-alanine L-RG and 9.7% -15.4% of dopamine hydrochloride C8H12ClNO2The balance of water; weight percent wt.%; the preparation method of the adhesive specifically comprises the following steps:
1) placing the animal glue BG and water in a three-neck flask, heating in a water bath at 50 ℃, mechanically stirring for 30min at 100r/min, and slowly adding 100mL of 1mol/L citric acid or tartaric acid or malic acid to obtain yellow bone glue solution;
2) slowly adding 100mL of 1mol/L hydrolytic agent into the yellow bone glue solution in the step 1), and continuously mechanically stirring for 40min at 100r/min in a water bath at 50 ℃ to obtain a bone glue hydrolytic solution;
3) placing the bone glue hydrolysis solution in the step 2) in an oil bath kettle at 70 ℃, slowly adding 3-sulfo-alanine L-RG powder, mechanically stirring for 5 hours at 250r/min, and filtering while hot to remove incompletely dissolved bone glue gel;
4) 1.2% strength N is introduced2Adding C into the filtrate obtained in the step 3)8H12ClNO2Stirring for 12 hours at 400r/min under the heating of 100 ℃ oil bath to obtain light yellow glue solution;
5) and (3) placing the light yellow glue solution in the step 4) into a rotary evaporator, performing rotary evaporation and concentration at 200r/min for 60min, and then placing into a vacuum drier at the temperature of-30 ℃ to freeze into powder, thus obtaining the animal glue binder for the cathode of the lithium-sulfur battery.
2. The preparation method of claim 1, wherein the hydrolytic reagent in the step 2) is one or two of tartaric acid, malic acid, citric acid, succinic acid, gluconic acid, citric acid and pyruvic acid natural organic acid.
3. The method according to claim 1, wherein 3-sulfo-alanine L-RG is selected as the modifier in step 3) because the carboxyl group of L-RG molecule can be amidated with the amino group of zoogum molecule, and-SO is present in 3-sulfo-alanine molecule3The H group can fix the cathode active material through substitution reaction, improving the utilization of the sulfur active material.
4. The preparation method according to claim 1, wherein dopamine C hydrochloride is selected in step 4)8H12ClNO2As another modifier, because C8H12ClNO2The amino group in the molecule can generate amidation reaction with the carboxyl group in the zoogum molecule, and the catechol amine group introduced into the dopamine hydrochloride can protect the structural integrity of the sulfur cathode.
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| US10079387B2 (en) * | 2014-02-26 | 2018-09-18 | The Regents Of The University Of California | Electrical conductive polymer binder for Si alloy materials |
| WO2017136409A1 (en) * | 2016-02-01 | 2017-08-10 | The Regents Of The University Of California | Functional polymer binder for sulfur cathode fabrication |
| KR102006720B1 (en) * | 2016-05-02 | 2019-08-02 | 주식회사 엘지화학 | Electrolyte Containing Polydopamine, And Lithium Sulfur Batteries Comprising The Same |
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| CN106390185A (en) * | 2016-12-02 | 2017-02-15 | 上海其胜生物制剂有限公司 | Preparation method of biological mimetic tissue adhesive |
| CN108155383A (en) * | 2017-11-29 | 2018-06-12 | 中山大学 | A kind of lithium-sulfur cell binding agent and preparation method thereof and lithium-sulphur cell positive electrode |
| CN108728110A (en) * | 2018-06-05 | 2018-11-02 | 佛山市陵谐环保科技有限公司 | A kind of soil-solidified-agent |
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