CN112011026B - Tung oil-based positive electrode binder for lithium-sulfur battery, positive electrode for lithium-sulfur battery and preparation method of positive electrode - Google Patents
Tung oil-based positive electrode binder for lithium-sulfur battery, positive electrode for lithium-sulfur battery and preparation method of positive electrode Download PDFInfo
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- H01M4/00—Electrodes
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- H—ELECTRICITY
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- H—ELECTRICITY
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- 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
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the field of energy high polymer materials, and particularly relates to a tung oil-based positive electrode binder for a lithium-sulfur battery, which is prepared from the following raw materials: 38-45 parts of tung oil-based glycol amine, 35-50 parts of diisocyanate, 5-20 parts of neutralizing agent and 5-27 parts of chain extender, and the preparation method comprises the following steps: (1) uniformly mixing tung oil-based glycol amine, diisocyanate and a chain extender for reaction; (2) adding a neutralizer into the obtained reaction liquid for reaction; (3) and adding deionized water into the obtained neutralization product for emulsification to obtain the product. The binder, the conductive agent and the active material are mixed to prepare electrode slurry, and the electrode slurry is coated on a current collector to prepare the anode of the lithium-sulfur battery so as to prepare the lithium-sulfur battery. The binder disclosed by the invention can improve the bonding capability, relieve the shuttle effect in the circulation process, and improve the integrity of the electrode, so that the long-circulation stability, the rate capability and the capacity retention rate of a sulfur-based positive electrode and other high-capacity electrodes are improved, and the mass specific capacity and the active substance loading capacity of the electrode are improved.
Description
Technical Field
The invention belongs to the field of energy high polymer materials, and particularly relates to a tung oil-based lithium-sulfur battery positive electrode binder subjected to in-situ cross-linking polymerization, a lithium-sulfur battery positive electrode and a preparation method thereof.
Background
The lithium-sulfur battery binder is a high molecular compound, although the mass proportion of the lithium-sulfur battery binder in the battery positive electrode material is less than 10%, the selection of the lithium-sulfur battery binder directly influences the exertion of the specific capacity of the battery, and the lithium-sulfur battery binder is one of indispensable materials for preparing an electrode plate. The main function of the adhesive is to tightly connect the active substance and the conductive agent in the electrode with the current collector, thereby reducing the impedance of the electrode, and simultaneously endowing the pole piece with good mechanical property and processability, which is easy for the requirement of actual production. The lithium sulfur battery has the following problems during use: (1) the lithium sulfide is dissolved in the electrolyte to generate a shuttle effect; (2) the volume of the sulfur anode is changed continuously in the lithiation process, so that the electrode structure is unstable and broken; (3) the sulfur particles are insulators, and have low electronic conductivity and high resistance. These problems result in a battery that decays more rapidly during charging and discharging. Therefore, a binder suitable for a lithium sulfur battery needs to satisfy the following conditions: (1) inhibiting the dissolution of lithium polysulfides in the electrolyte; (2) the volume change generated by the sulfur anode in the charging and discharging process can be borne; (3) the conductivity of the sulfur positive electrode is improved.
Polyvinylidene fluoride (PVDF) has been widely used in lithium sulfur batteries as one of the most common binders. However, the non-functional linear structure of PVDF is very weak in ability to absorb polysulfide, and has very high viscosity in use, and a large amount of toxic organic solvent N-methyl-2-pyrrolidone (NMP) is needed for dilution, which is not good for manufacturing the electrode plate and is harmful to environment and users. The biomass-derived molecular polymer has wide sources, low price and environmental friendliness, and rich hydrophilic polar groups in the molecular structure of the polymer become one of important development directions of high-performance binders. Therefore, there is still a need to develop a polymer binder using biomass as a monomer to realize its commercial application in a binder for lithium-sulfur batteries. Biomass materials, such as chitosan, lignin, carrageenan, and the like, are good raw materials for preparing sulfur positive electrode polymer binders because they are renewable, abundant, inexpensive, and readily available and their structures are rich in polar groups. However, the bonding strength, adsorption kinetics and mechanical properties of these raw materials prepared binders are currently insufficient to meet the requirements of a wide range of practical applications. Binders with strong bond strength, high thermal/electrochemical stability and sufficient mechanical properties still need to be developed to meet commercial production needs.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the prepared tung oil-based lithium-sulfur battery positive binder through in-situ crosslinking polymerization can improve the bonding capacity of the binder, so that an active substance, a current collector and the binder form a firmer whole, the shuttle effect in the circulation process is relieved, the integrity of an electrode is improved, the long-cycle stability, the rate capability and the capacity retention rate of a sulfur-based positive electrode and other high-capacity electrodes are improved, and the specific mass capacity and the active substance carrying capacity of the electrode are improved.
The purpose of the invention is realized by the following technical scheme:
the positive electrode binder of the tung oil-based lithium-sulfur battery is prepared from the following raw materials in parts by weight: 38-45 parts of tung oil-based glycol amine, 35-50 parts of diisocyanate, 5-20 parts of a neutralizer and 5-27 parts of a chain extender.
Further, the synthesis method of the tung oil-based glycol amine refers to CN 201811011744.8.
Further, the diisocyanate is aromatic diisocyanate, aliphatic diisocyanate, and alicyclic diisocyanate.
Further, the neutralizing agent is phytic acid, hydrochloric acid, lysine or acetic acid, preferably phytic acid.
Further, the chain extender is N-methyldiethanolamine, hexamethylenediamine or 2, 3-dibromo succinic acid.
The preparation method of the tung oil-based lithium-sulfur battery positive electrode binder comprises the following steps:
(1) adding tung oil-based glycol amine, diisocyanate and a chain extender into a container in a certain proportion, uniformly mixing, reacting at 50-80 ℃, synthesizing to obtain-NCO-terminated viscous prepolymer, and adding a proper amount of butanone to reduce the viscosity of the prepolymer;
(2) adding the neutralizer into the reaction liquid obtained in the step (1) for neutralization reaction;
(3) and (3) adding deionized water into the neutralized product obtained in the step (2) for emulsification (2-4 hours), and removing butanone after reaction (a rotary evaporator).
The positive electrode binder of the tung oil-based lithium-sulfur battery contains a large amount of heteroatoms and abundant polar groups, including phosphorus-oxygen functional groups, carbamate groups and quaternary ammonium ions; the fresh binder solid content is adjusted to 5-35% by the water addition amount during emulsification.
The tung oil-based glycol amine used in the invention is used as a comb-shaped soft segment structure formed by soft segments to endow the WPU with flexible tensile capability, so that the WPU can cope with current impact during charging and discharging.
The invention also provides a lithium-sulfur battery positive electrode, which comprises any one of the tung oil-based lithium-sulfur battery positive electrode binders. The preparation method of the lithium-sulfur battery positive electrode comprises the following steps: and mixing the tung oil-based lithium-sulfur battery positive electrode binder with an active material and a conductive agent to prepare electrode slurry, coating the electrode slurry on a current collector, and drying to obtain the lithium-sulfur battery positive electrode. And punching the obtained positive electrode of the lithium-sulfur battery into a pole piece by using a punching machine, drying the surface moisture, transferring into a glove box, weighing and assembling to obtain the lithium-sulfur battery.
Furthermore, in the raw materials, the tung oil-based lithium-sulfur battery positive electrode binder (based on solid content) accounts for 5-15 wt%, the conductive agent accounts for 28-32 wt%, and the active material accounts for 57-67 wt%.
Further, the active material is sublimed sulfur, lithium polysulfide or organic sulfide; the conductive agent is a substance capable of increasing conductivity and is at least one of acetylene black, conductive graphite, SuperP, Ketjen black and carbon nanotubes; the current collector is copper foil, aluminum foil, foam copper, non-woven fabric plated with copper, foam nickel or non-woven fabric plated with nickel.
Further, the pole piece is dried to remove moisture contained in the electrode material, and the used method comprises a vacuum drying method; the temperature for drying the pole piece is determined according to the physical and chemical properties of the battery material, and is not too high or too low.
Tung oil is an ester formed by glycerol and fatty acid, and the important lipid component of the tung oil is tung acid containing conjugated double bonds in the fatty acid in the triglyceride of tung oil acid. The structure of the long-chain fatty acid can effectively improve the flexibility and the ductility of the binder so as to adapt to the volume change of the sulfur anode material in the charge-discharge process. Meanwhile, the high-activity conjugated double bond structure is beneficial to the rapid polymerization of the slurry into a dense cured film, so that a good in-situ polymerization three-dimensional framework is provided, and the volume change of the sulfur anode material in the charging and discharging process is further borne. Therefore, the above-mentioned various problems occurring in lithium sulfur batteries have been addressed by developing a water-soluble multifunctional double cross-linked polymer network binder (WPU) by means of in-situ cross-linking. The low viscosity of the WPU is beneficial to coating of pole pieces, and the effective physical connection and high mechanical strength between molecules in the positive binder structure are endowed by the double-crosslinked network structure, so that the positive material is tightly connected, the integrity of the sulfur positive material can be effectively maintained, and meanwhile, the transmission path of ions and electrons in the battery is shortened.
Electrochemical test results show that the initial discharge specific capacity of a battery using commercial PVDF as a sulfur positive electrode is 809mAh/g under the current density of 0.5C, the battery discharge specific capacity is greatly attenuated to 484 mAh/g after 239 cycles of circulation, the sulfur positive electrode prepared by the binder is used for assembling a lithium-sulfur battery, the initial discharge specific capacity is up to 1051 mAh/g under the same condition, the mass specific capacity is still up to 632 mAh/g after 600 cycles of circulation, the capacity retention rate is 60.1%, the electrochemical performance is remarkably improved, and meanwhile, the rate capability of the lithium-sulfur battery based on the binder is also improved. Furthermore, the WPU sulfur positive electrode based all-cell provided 1.3 mAh cm over 300 cycles-2The capacity retention rate of each cycle is as high as 99.83 percent. This new binder design strategy is crucial for the development of high energy density lithium sulfur batteries.
When the in-situ cross-linked polymerized tung oil-based binder prepared by the invention is applied to a sulfur positive electrode, the electrochemical properties such as the cycle performance, the rate performance and the like of the sulfur electrode can be improved, but the application of the binder prepared by the invention is not limited to the sulfur electrode, and the binder can also be applied to other lithium ion battery electrode materials, and comprises the following steps: lithium cobaltate, lithium iron phosphate anode material, nickel cobalt lithium manganate ternary anode material, silicon-based cathode material, graphite cathode material and the like, and has wide application range.
Compared with the prior art, the invention has the following advantages and technical effects:
the lithium-sulfur battery prepared by mixing the in-situ crosslinking polymerized tung oil-based binder, the active substance and the conductive agent has good electrochemical performance, and compared with some reported binders, the cycle performance and the high-rate charge and discharge performance of the lithium-sulfur battery are greatly improved.
The method disclosed by the invention has the advantages of low-cost and easily-obtained raw materials, simplicity in operation, easiness in implementation, capability of operating at room temperature, energy conservation, no toxic substance generation and environmental friendliness.
The method has the advantages of simple process, low operation and equipment cost, economy and environmental protection, is expected to realize industrial production through simple adjustment, and has great market application potential.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto. Other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principles of the invention are intended to be included within the scope of the invention.
Example 1
A preparation method of tung oil-based positive electrode binder for lithium-sulfur batteries neutralized by hydrochloric acid comprises the following steps:
(1) under the action of mechanical stirring, 3g of tung oil-based glycol amine, 3.7g of isophorone diisocyanate and 1.1g N-methyldiethanolamine are added into a flask and heated to 78 ℃ for reaction to obtain a viscous prepolymer terminated by-NCO;
(2) after the step (1) is finished, adding 5mL of butanone into the solution in the step (1) to reduce the viscosity of the product, and continuing stirring;
(3) cooling the reaction system in the step (2) to room temperature;
(4) adding 0.9g of hydrochloric acid into the prepolymer obtained in the step (3), and continuing stirring for half an hour;
(5) adding 30mL of deionized water into the step (4), and continuously stirring at a high speed for 2h to obtain an emulsified aqueous dispersion;
(6) and (4) performing rotary evaporation on the aqueous dispersion obtained in the step (5) to remove butanone, thus obtaining the tung oil-based lithium sulfur battery positive electrode binder.
Example 2
A preparation method of a tung oil-based positive electrode binder for a lithium-sulfur battery neutralized by phytic acid comprises the following steps:
(1) under the action of mechanical stirring, 3g of tung oil-based glycol amine, 3.7g of isophorone diisocyanate and 1.1g N-methyldiethanolamine are added into a flask and heated to 78 ℃ for reaction to obtain a viscous prepolymer terminated by-NCO;
(2) after the step (1) is finished, adding 5mL of butanone solvent into the solution in the step (1) to reduce the viscosity of the product, and continuing stirring;
(3) cooling the reaction system in the step (2) to room temperature;
(4) adding 0.75g of phytic acid into the prepolymer obtained in the step (3), and continuing stirring for half an hour;
(5) adding 30mL of deionized water into the step (4), and continuously stirring at a high speed for 2h to obtain an emulsified aqueous dispersion;
(6) and (4) performing rotary evaporation on the aqueous dispersion obtained in the step (5) to remove butanone, thus obtaining the tung oil-based lithium-sulfur battery positive electrode binder.
Example 3
A preparation method of a lysine-neutralized tung oil-based positive electrode binder for a lithium-sulfur battery comprises the following steps:
(1) under the action of mechanical stirring, 3g of tung oil-based glycol amine, 3.7g of isophorone diisocyanate and 1.1g N-methyldiethanolamine are added into a flask and heated to 78 ℃ for reaction to obtain a viscous prepolymer terminated by-NCO;
(2) after the step (1) is finished, adding 5mL of butanone into the solution in the step (1) to reduce the viscosity of the product, and continuing stirring;
(3) cooling the reaction system in the step (2) to room temperature;
(4) adding 1.32g of lysine into the prepolymer obtained in the step (3), and continuing stirring for half an hour;
(5) adding 30mL of deionized water into the step (4), and continuously stirring at a high speed for 2h to obtain an emulsified aqueous dispersion;
(6) and (4) performing rotary evaporation on the aqueous dispersion obtained in the step (5) to remove butanone, thus obtaining the tung oil-based lithium-sulfur battery positive electrode binder.
Example 4
A preparation method of a tung oil-based positive electrode binder for a lithium-sulfur battery neutralized by acetic acid comprises the following steps:
(1) under the action of mechanical stirring, 3g of tung oil-based glycol amine, 3.7g of isophorone diisocyanate and 1.1g N-methyldiethanolamine are added into a flask and heated to 78 ℃ for reaction to obtain a viscous prepolymer terminated by-NCO;
(2) after the step (1) is finished, adding 5mL of butanone into the solution in the step (1) to reduce the viscosity of the product, and continuing stirring;
(3) cooling the reaction system in the step (2) to room temperature;
(4) adding 0.97g of acetic acid into the prepolymer obtained in the step (3), and continuing stirring for half an hour;
(5) adding 30mL of deionized water into the step (4), and continuously stirring at a high speed for 2h to obtain an emulsified aqueous dispersion;
(6) and (4) performing rotary evaporation on the aqueous dispersion obtained in the step (5) to remove butanone to obtain the tung oil base lithium sulfur battery positive electrode binder.
Example 5
A preparation method of a citric acid neutralized tung oil based positive electrode binder for a lithium-sulfur battery comprises the following steps:
(1) under the action of mechanical stirring, 3g of tung oil-based glycol amine, 3.7g of isophorone diisocyanate and 1.1g N-methyldiethanolamine are added into a flask and heated to 78 ℃ for reaction to obtain a viscous prepolymer terminated by-NCO;
(2) after the step (1) is finished, adding 5mL of butanone into the solution in the step (1) to reduce the viscosity of the product, and continuing stirring;
(3) cooling the reaction system in the step (2) to room temperature;
(4) adding 1.74g of citric acid into the prepolymer obtained in the step (3), and continuing stirring for half an hour;
(5) adding 30mL of deionized water into the step (4), and continuously stirring at a high speed for 2h to obtain an emulsified aqueous dispersion;
(6) and (4) performing rotary evaporation on the aqueous dispersion obtained in the step (5) to remove butanone, thus obtaining the tung oil-based lithium-sulfur battery positive electrode binder.
Example 6
The application of the tung oil-based positive electrode binder of the lithium-sulfur battery neutralized by hydrochloric acid in the lithium-sulfur battery comprises the following specific processes:
(1) uniformly mixing 0.7g of tung oil-based lithium-sulfur battery positive binder (with the solid content of 30 percent), 1.2g of sublimed sulfur and 0.6g of conductive agent (50 wt percent of SuperP and 50wt percent of Ketjen black) to obtain electrode slurry, adjusting the viscosity of the slurry by adding deionized water, coating the slurry on a current collector by using a scraper, and then airing at room temperature to obtain a sulfur positive electrode;
(2) punching the sulfur positive electrode obtained in the step (1) into a pole piece with a certain diameter by using a punching machine, and drying the pole piece in a vacuum drying oven at 120 ℃ for 12 hours;
(3) and (3) moving the electrode pole pieces obtained in the step (2) into a glove box filled with argon, weighing one by one, recording, and assembling into a battery in the glove box to obtain the lithium-sulfur battery.
Example 7
The application of the tung oil-based positive electrode binder for the lithium-sulfur battery neutralized by phytic acid in the lithium-sulfur battery specifically comprises the following steps:
(1) uniformly mixing 0.7g of tung oil-based lithium-sulfur battery positive binder (with the solid content of 30%) with 1.2g of sulfur powder sublimed sulfur and 0.6g of conductive agent (50 wt% of SuperP +50wt% of Ketjen black) to obtain electrode slurry, adjusting the viscosity of the slurry by adding deionized water, coating the slurry on a current collector by using a scraper, and then airing at room temperature to obtain a sulfur positive electrode;
(2) punching the sulfur positive electrode obtained in the step (1) into a pole piece with a certain diameter by using a punching machine, and drying the pole piece in a vacuum drying oven at 120 ℃ for 12 hours;
(3) and (3) moving the electrode pole pieces obtained in the step (2) into a glove box filled with argon, weighing one by one, recording, and assembling into a battery in the glove box to obtain the lithium-sulfur battery.
Example 8
The application of the lysine-neutralized tung oil-based positive electrode binder for the lithium-sulfur battery in the lithium-sulfur battery comprises the following specific processes:
(1) uniformly mixing 0.7g of tung oil-based lithium-sulfur battery positive binder (with the solid content of 30 percent), 1.2g of sublimed sulfur and 0.6g of conductive agent (50 wt percent of SuperP and 50wt percent of Ketjen black) to obtain electrode slurry, adjusting the viscosity of the slurry by adding deionized water, coating the slurry on a current collector by using a scraper, and then airing at room temperature to obtain a sulfur positive electrode;
(2) punching the sulfur positive electrode obtained in the step (1) into a pole piece with a certain diameter by using a punching machine, and drying the pole piece in a vacuum drying oven at 120 ℃ for 12 hours;
(3) and (3) moving the electrode pole pieces obtained in the step (2) into a glove box filled with argon, weighing one by one, recording, and assembling into a battery in the glove box to obtain the lithium-sulfur battery.
Example 9
The application of the positive electrode binder of the tung oil-based lithium-sulfur battery neutralized by acetic acid in the lithium-sulfur battery comprises the following specific processes:
(1) uniformly mixing 0.7g of tung oil-based lithium-sulfur battery positive binder (with the solid content of 30 percent), 1.2g of sublimed sulfur and 0.6g of conductive agent (50 wt percent of SuperP and 50wt percent of Ketjen black) to obtain electrode slurry, adjusting the viscosity of the slurry by adding deionized water, coating the slurry on a current collector by using a scraper, and then airing at room temperature to obtain a sulfur positive electrode;
(2) punching the sulfur positive electrode obtained in the step (1) into a pole piece with a certain diameter by using a punching machine, and drying the pole piece in a vacuum drying oven at 120 ℃ for 24 hours;
(3) and (3) moving the electrode pole pieces obtained in the step (2) into a glove box filled with argon, weighing one by one, recording, and assembling into a battery in the glove box to obtain the lithium-sulfur battery.
For the lithium-sulfur battery assembled with the tung oil-based lithium-sulfur battery positive binder neutralized with hydrochloric acid in example 6, the initial specific discharge capacity was 812 mAh/g at a current density of 0.5C, and the specific mass capacity was 401 mAh/g after 600 cycles. The initial specific discharge capacity of a battery using commercial PVDF as a sulfur positive electrode is 809mAh/g under the current density of 0.5C, after the battery is circulated for 239 circles, the specific discharge capacity of the battery is greatly attenuated to 484 mAh/g, for a lithium sulfur battery assembled by using the tung oil-based lithium sulfur battery positive electrode binder neutralized by phytic acid in the embodiment 7, under the same condition, the initial specific discharge capacity is up to 1053 mAh/g, after the battery is circulated for 600 weeks, the specific mass capacity is still up to 632 mAh/g, and the charge and discharge performance of the battery is remarkably improved.
Claims (10)
1. The tung oil-based positive electrode binder for the lithium-sulfur battery is characterized by being prepared from the following raw materials in parts by weight: 38-45 parts of tung oil-based glycol amine, 35-50 parts of diisocyanate, 5-20 parts of a neutralizer and 5-27 parts of a chain extender;
the molecular structure of the tung oil-based glycol amine is shown as the following formula:
2. the positive electrode binder for tung oil-based lithium sulfur batteries according to claim 1, characterized in that: the diisocyanate is aromatic diisocyanate, aliphatic diisocyanate or alicyclic diisocyanate.
3. The positive electrode binder for tung oil-based lithium sulfur batteries according to claim 1, characterized in that: the neutralizer is phytic acid, hydrochloric acid, lysine or acetic acid.
4. The positive electrode binder for tung oil-based lithium sulfur batteries according to claim 1, characterized in that: the chain extender is N-methyldiethanolamine, hexamethylenediamine or 2, 3-dibromo succinic acid.
5. The method for preparing the positive electrode binder for tung oil-based lithium sulfur batteries as claimed in any one of claims 1 to 4, comprising the steps of:
(1) uniformly mixing the tung oil-based glycol amine, diisocyanate and a chain extender, reacting at 50-80 ℃, and adding a proper amount of butanone to reduce the viscosity after the reaction;
(2) adding the neutralizer into the reaction liquid obtained in the step (1) for neutralization reaction;
(3) and (3) adding deionized water into the neutralization product obtained in the step (2) for emulsification, and removing butanone after reaction to obtain the product.
6. A lithium sulfur battery positive electrode, characterized in that: a positive electrode binder for tung oil-based lithium sulfur batteries comprising any one of claims 1 to 4.
7. The positive electrode for a lithium-sulfur battery according to claim 6, wherein the solid content comprises the following raw materials in percentage by weight: 5-15% of tung oil-based lithium-sulfur battery positive binder, 28-32% of conductive agent and 57-67% of active material.
8. The lithium sulfur battery positive electrode according to claim 7, characterized in that: the active material is sublimed sulfur, lithium polysulfide or an organosulfide.
9. The lithium sulfur battery positive electrode according to claim 7, characterized in that: the conductive agent is at least one of acetylene black, conductive graphite, SuperP, Ketjen black and carbon nanotubes.
10. A method of making a positive electrode for a lithium sulfur battery as defined in any one of claims 7 to 9, comprising the steps of: and mixing the tung oil-based lithium-sulfur battery positive electrode binder with the active material and the conductive agent to prepare electrode slurry, coating the electrode slurry on a current collector, and drying to obtain the lithium-sulfur battery positive electrode.
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