CN111961438B - Electrostatic combined aqueous binder and application thereof in lithium ion battery - Google Patents

Electrostatic combined aqueous binder and application thereof in lithium ion battery Download PDF

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CN111961438B
CN111961438B CN202010869587.5A CN202010869587A CN111961438B CN 111961438 B CN111961438 B CN 111961438B CN 202010869587 A CN202010869587 A CN 202010869587A CN 111961438 B CN111961438 B CN 111961438B
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polyphosphoric acid
solution
lithium
sulfur
positive electrode
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CN111961438A (en
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杨卓鸿
刘飞
杨宇
卢梁美
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South China Agricultural University
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J189/00—Adhesives based on proteins; Adhesives based on derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/04—Non-macromolecular additives inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/329—Phosphorus containing acids
    • 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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  • Secondary Cells (AREA)

Abstract

The invention discloses an electrostatic binding type aqueous binder, which mainly comprises a compound containing a phosphate group and a compound containing an amino group according to the mass ratio of 0.5:1-2:1, and when the two are respectively prepared into solutions to be mixed for use, the two compounds can be bound through electrostatic adsorption to form a binder with high binding power and strong binding performance, and the binder can be used as an aqueous binder. The electrostatic binding type aqueous binder provided by the invention has obvious binding power, and the introduction of the phosphate group can effectively improve the ionic conductivity, so that the electrostatic binding type aqueous binder is beneficial to improving the electrode cycle performance and the high-rate charge and discharge performance of the lithium ion battery when being applied to the assembly of the lithium ion battery. The electrostatic combination type aqueous binder provided by the invention can be applied to the preparation of lithium ion battery electrodes, and the prepared electrodes have better structural integrity and stability and good cycling stability.

Description

Electrostatic combined aqueous binder and application thereof in lithium ion battery
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to an electrostatic combination type aqueous binder and application thereof in preparation of a lithium ion battery electrode.
Background
The lithium-sulfur battery has the advantages of high theoretical energy density, low price of sulfur anode material, wide source, no toxicity and the like. However, the following problems of the lithium sulfur battery, which have not been well solved, have greatly hindered the practical application and industrial development of the lithium sulfur battery: (1) the shuttle effect of lithium polysulfide in the charging and discharging processes of the lithium-sulfur battery; (2) due to elemental sulphur and its discharge products (Li)2S2And Li2S) are both electrons andion insulator (5X 10)-30S/cm, 25 ℃), resulting in low utilization rate of active substances and poor rate performance when the material is used as a positive electrode material; (3) density difference between sulfur and lithium sulfide (2.03 and 1.66g/cm, respectively)3) The volume expansion of elemental sulfur in the charging and discharging process is about 80% to form lithium sulfide, so that the huge volume change can cause the damage of the sulfur anode structure, and simultaneously, the connection between sulfur and a conductive agent is lost, so that isolated sulfur can not participate in the subsequent electrochemical reaction, and the irreversible capacity loss of the sulfur anode is caused.
In a lithium-sulfur battery, the integrity of the electrode structure and the stability thereof directly affect the cycle performance of the battery, and the change of the electrode structure is very easy to cause the changes of internal resistance, ion diffusion resistance and cycle stability. As an important component of sulfur positive electrodes, the binder is capable of inhibiting diffusion of lithium polysulfide in the electrolyte and protecting the positive electrode structural integrity. As a binder for lithium sulfur batteries, it is generally required to have the following properties: (1) the binder can keep the stability of structure and binding power in the battery cycle process, and has low swelling in electrolyte; (2) the adhesive can play a strong enough bonding role for the active material, namely, has strong enough cohesive force; (3) ensuring that the active substance and the current collector have enough strong adhesive force, namely enough strong adhesive force; (4) have relatively high electronic and ionic conductivity, i.e., low resistance; (5) the active substance is strongly limited, so that the active substance cannot generate larger volume change, the structure of the positive electrode can be protected, and the stability of the positive electrode can be maintained; (6) has certain inhibition effect on shuttle penetration effect and the like.
Polyvinylidene fluoride (PVDF) is currently the most widely used oil-soluble binder for lithium-sulfur batteries, has a certain adhesive strength and high chemical stability, and can swell the electrolyte to improve the ionic conductivity of the electrode. On one hand, the PVDF excessively swells electrolyte and is gelated to form viscous liquid, so that the active substance is separated from a conductive network, the impedance is increased, and the capacity loss is caused; on the other hand, an organic solvent N-methyl pyrrolidone (NMP) is needed in the PVDF dissolving process, the NMP has good dissolving capacity, but has a high boiling point (203 ℃), so that the electrode drying conditions are harsh (the drying temperature is 120 ℃), the electrode structure can be damaged, meanwhile, the NMP has certain toxicity, the harm can be caused to a human fertility system, and the cost can be increased due to the fact that an NMP recovery device is needed to be additionally arranged in the battery manufacturing process.
Chinese patent application CN111430716A discloses an aqueous soy protein based supramolecular sulfur anode binder, a preparation method and an application thereof, the binder comprises phosphorylated soy protein, a lithium ion transmission promoter and a physical cross-linking agent, has excellent lithium ion conductivity and strong lithium polysulfide adsorption, but the preparation method is complex, and the binding power of the binder is still to be improved.
Disclosure of Invention
The invention aims to provide a water-based binder which has strong binding power, so that active substances, current collectors and the like in an electrode can be mutually combined into a firm whole through the binder, the integrity of the electrode is improved, the shuttle effect in the cycle process of a lithium-sulfur battery can be relieved, the long cycle stability, the rate capability and the capacity retention rate of the electrode are further improved, and the specific mass capacity and the active substance carrying capacity of the electrode are improved.
According to an aspect of the present invention, there is provided an electrostatically binding type aqueous adhesive comprising a component a and a component B which are independently present, wherein:
the component A comprises a compound containing a phosphate group and/or a compound solution containing a phosphate group; the concentration of the phosphoric acid group-containing compound solution is 1 to 10 wt%;
the component B comprises an amino group-containing compound and/or an amino group-containing compound solution; the concentration of the amino group-containing compound solution is 1 to 10 wt%;
when the phosphoric acid group-containing compound and the amino group-containing compound are used, the component A and the component B are mixed according to the mass ratio of 0.5:1-2:1, and when the component A and/or the component B are compounds, the compounds are prepared into a solution with the concentration of 1-10wt% and then mixed.
When the compound containing the phosphate group and the compound containing the amino group are respectively prepared into solutions and then mixed, the phosphate group and the compound containing the amino group can be combined through electrostatic adsorption to form a binder with high binding power and strong binding performance, and the binder can be used as an aqueous binder. According to the electrostatic bonding type aqueous binder provided by the invention, the introduction of amino groups can improve the performance of a polymer binder, and the introduction of phosphate groups can improve the ionic conductivity, so that the electrochemical performance of an electrode material of a lithium ion battery under a long-term circulation condition can be improved.
In some embodiments, the phosphate group-containing compound may be selected from one or both of polyphosphoric acid and phytic acid; the compound having an amino group may be at least one selected from silk fibroin, collagen, soybean protein and bovine serum albumin.
In some embodiments, the phosphate group-containing compound may be polyphosphoric acid and the amino group-containing compound may be silk fibroin. The silk fibroin solution and the polyphosphoric acid solution are combined in an electrostatic adsorption mode, and strong polar phosphate groups and amino groups are introduced into the binder, so that the electrochemical performance of the binder can be obviously improved, and the long-period cycle performance of a sulfur electrode assembled by the polyphosphoric acid and silk fibroin electrostatic combined aqueous binder at higher current density and the charge and discharge performance of the sulfur electrode under high-rate current are improved.
In some embodiments, the method for preparing the electrostatic binding type aqueous binder comprising polyphosphoric acid and silk fibroin comprises the following steps:
(1) adding silkworm cocoon into sodium carbonate solution with concentration of 4-10g/L according to solid-to-liquid ratio of 10-50g/L, heating to 80-100 deg.C, maintaining for 1-2 hr, filtering, and drying the filter residue to obtain fibroin;
(2) adding silk fibroin into 7-10M lithium bromide solution, dissolving, filtering with filter cloth, and dialyzing with dialysis membrane with molecular weight cutoff of 3.5-10kDa to obtain 1-10wt% silk fibroin solution;
(3) taking polyphosphoric acid, and independently packaging the polyphosphoric acid and the silk fibroin solution to obtain an electrostatic binding type aqueous binder, wherein the polyphosphoric acid is taken according to the mass ratio of the polyphosphoric acid to the silk fibroin of 0.5:1-2:1 when the electrostatic binding type aqueous binder is used, then the polyphosphoric acid is added with water to prepare a polyphosphoric acid solution with the concentration of 1-10wt%, and the polyphosphoric acid solution is mixed with the silk fibroin solution; or
And (2) adding water into polyphosphoric acid to prepare a polyphosphoric acid solution with the concentration of 1-10wt%, and subpackaging the polyphosphoric acid solution and the silk fibroin solution respectively to obtain the electrostatic binding type aqueous binder, wherein the polyphosphoric acid solution and the silk fibroin solution are mixed according to the mass ratio of polyphosphoric acid to silk fibroin of 0.5:1-2:1 when in use.
According to a second aspect of the present invention, there is provided the use of an electrostatically bound aqueous binder of the present invention in the preparation of an electrode for a lithium ion battery.
When the electrostatic bonding type aqueous binder provided 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 electrostatic bonding type binder provided by the invention is not limited to the sulfur electrode, and the electrostatic bonding type aqueous binder can also be applied to other lithium ion battery electrodes, including but not limited to: lithium cobaltate positive pole, lithium iron phosphate positive pole, lithium cobalt manganese oxide ternary positive pole, silicon-based negative pole, graphite negative pole, etc., and the application range is wide.
According to a third aspect of the present invention, there is provided a sulfur positive electrode of a lithium sulfur battery, comprising a current collector and a positive electrode material coated on the current collector, wherein the positive electrode material comprises the following components in parts by weight: 6-8 parts of active material, 1-4 parts of conductive agent and 0.5-1.5 parts of binder provided by the invention in parts by weight calculated according to solid content.
The electrostatic combination type aqueous binder provided by the invention has strong binding capacity, has a strong enough binding effect on an active material and a conductive agent, and can enable the sulfur positive electrode material to be firmly bound on a current collector when the positive electrode material is coated on the current collector to prepare a sulfur positive electrode, so that the active material, the conductive agent, the binder and the current collector can be combined into a firm whole, the integrity of the sulfur positive electrode structure and the stability of the sulfur positive electrode can be effectively maintained, and the cycle stability, the rate capability and the capacity retention rate of the sulfur positive electrode can be effectively improved.
In some embodiments, the active material may be selected from sublimed sulfur, Li2S2、Li2S4、Li2S6、Li2S8At least one of (1).
In some embodiments, the conductive agent may be selected from at least one of acetylene black, conductive graphite, Super P, ketjen black, and carbon nanotubes.
In some embodiments, the current collector may be selected from one of copper foil, aluminum foil, copper foam, copper-plated non-woven fabric, nickel foam, nickel-plated non-woven fabric.
According to a fourth aspect of the present invention, there is provided a method for producing a sulfur positive electrode, comprising the steps of:
(1) ball-milling and mixing a compound solution containing a phosphate group, a compound solution containing an amino group, an active material and a conductive agent to obtain electrode slurry;
(2) and coating the electrode slurry on a current collector, drying, then preparing a pole piece, and drying to obtain the sulfur positive electrode.
In the process of preparing the sulfur anode by using the electrostatic combined type aqueous binder, the solvent can be water, an organic solvent is not needed, no toxic substance is generated in the preparation process, the preparation process is simple, the operation and equipment cost is low, and the preparation method is economic and environment-friendly.
In some embodiments, the drying method may be vacuum drying. The drying is performed for the purpose of removing moisture contained in the electrode material, and the temperature used in the drying is not too high nor too low depending on the physical and chemical properties of the battery material.
According to a fifth aspect of the present invention, there is provided a lithium sulfur battery comprising the sulfur positive electrode provided by the present invention.
In some embodiments, a lithium sulfur battery includes a polymer separator, an electrolyte, and a lithium negative electrode in addition to the sulfur positive electrode provided by the present invention. And assembling the sulfur positive electrode, the polymer diaphragm, the electrolyte and the lithium negative electrode into a battery in a glove box, so as to obtain the lithium-sulfur battery.
Compared with the lithium-sulfur battery assembled by using the PVDF binder, the lithium-sulfur battery using the electrostatic binding type aqueous binder provided by the invention has the advantages that the initial discharge specific capacity is remarkably improved, the capacity retention rate is about 70% after the lithium-sulfur battery is cycled for 200 weeks, and the cycling stability is remarkably improved. In addition, the rate performance of a lithium-sulfur battery using the electrostatically binding aqueous binder of the present invention can also be improved.
Compared with the prior art, the invention has the beneficial effects that:
(1) in the electrostatic binding type aqueous binder provided by the invention, phosphate groups and amino groups are bound in an electrostatic adsorption mode, the binding power is obviously improved, and the introduction of the phosphate groups can effectively improve the ionic conductivity, so that the improvement of the cycle performance and the high-rate charge and discharge performance of a lithium ion battery electrode is facilitated;
(2) the sulfur positive electrode prepared by the electrostatic combined type aqueous binder provided by the invention has better electrode structural integrity and stability and good cycling stability;
(3) the electrostatic combination type aqueous binder provided by the invention is used for preparing the sulfur anode of the lithium-sulfur battery, the raw materials are cheap and easy to obtain, the method is simple, the operation and equipment cost is low, and an organic solvent is not needed in the preparation process, so that the method is economic and environment-friendly.
Detailed Description
The present invention will be described in further detail with reference to embodiments. The examples are for illustration only and do not limit the invention in any way. Unless otherwise specified, the starting materials and reagents used in the examples are conventional products commercially available; the experimental methods of specific conditions not noted in the examples are conventional methods and conventional conditions well known in the art.
Example 1 preparation of silk fibroin solution
The method comprises the following steps:
(1) under the action of magnetic stirring, 5.3g of sodium carbonate is added into deionized water with the amount of 1LpH being between 6.8 and 7.4 to be dissolved, so as to obtain sodium carbonate solution;
(2) adding silkworm cocoon at solid-to-liquid ratio of 10-50g/L into sodium carbonate solution, heating to 80-100 deg.C, maintaining for 1-2 hr, and stirring occasionally; then filtering, and drying the filter residue to obtain fibroin;
(3) dissolving 4g of silk fibroin in 16mL of 9.3M lithium bromide solution (containing 12.95g of lithium bromide); then filtering the dissolved solution through filter cloth and dialyzing to obtain silk fibroin solution with the concentration of 2.5 wt%; wherein, the dialysis is deionized water dialysis, the dialysis treatment time is 3-5 days according to the standard that the dialysis bag is not broken by expansion, and the deionized water is replaced during the dialysis; the cut-off molecular weight of the dialysis bag is 3.5-10 kDa.
Example 2 electrostatically bonding type aqueous adhesive
The electrostatically binding type aqueous adhesive of this example comprises polyphosphoric acid and silk fibroin solution at a concentration of 2.5 wt% each separately dispensed.
When the silk fibroin solution is used, polyphosphoric acid is taken according to the mass ratio of polyphosphoric acid to silk fibroin of 0.5:1-2:1, then the polyphosphoric acid is added with deionized water to prepare polyphosphoric acid solution with the concentration of 1-10wt%, and the polyphosphoric acid solution is mixed with the silk fibroin solution.
Example 3 electrostatically bonding type aqueous adhesive
The electrostatically binding type aqueous binder of this example comprises phytic acid and silk fibroin solution at a concentration of 2.5 wt% each separately dispensed.
When in use, the phytic acid is taken according to the mass ratio of the phytic acid to the silk fibroin of 0.5:1-2:1, then the phytic acid is added with deionized water to prepare a phytic acid solution with the concentration of 1-10wt%, and the phytic acid solution is mixed with the silk fibroin solution.
Example 4 electrostatically bonding type aqueous adhesive
The electrostatically binding type aqueous adhesive of this example comprises polyphosphoric acid and soybean protein each separately dispensed.
When the soybean protein solution is used, polyphosphoric acid and soybean protein are respectively taken according to the mass ratio of polyphosphoric acid to soybean protein of 0.5:1-2:1, deionized water is respectively added into the polyphosphoric acid and the soybean protein to prepare a polyphosphoric acid solution with the concentration of 1-10wt% and a soybean protein solution, and the polyphosphoric acid solution and the soybean protein solution are mixed to obtain the soybean protein solution.
Example 5 electrostatically joining type aqueous adhesive
This example of the electrostatically binding type aqueous adhesive comprises polyphosphoric acid and a collagen solution having a concentration of 3 wt% each separately dispensed.
When the collagen protein solution is used, polyphosphoric acid is taken according to the mass ratio of polyphosphoric acid to collagen of 0.5:1-2:1, the polyphosphoric acid is added with deionized water to prepare a polyphosphoric acid solution with the concentration of 1-10wt%, and the polyphosphoric acid solution and the collagen protein solution are mixed.
Example 6 electrostatically joining type aqueous adhesive
The electrostatically binding aqueous adhesive of this embodiment comprises polyphosphoric acid and bovine serum albumin separately dispensed from each other.
When the composite material is used, polyphosphoric acid and bovine serum albumin are respectively taken according to the mass ratio of polyphosphoric acid to bovine serum albumin of 0.5:1-2:1, deionized water is respectively added into the polyphosphoric acid and the bovine serum albumin to prepare polyphosphoric acid solution and bovine serum albumin solution with the concentration of 1-10wt%, and the polyphosphoric acid solution and the bovine serum albumin solution are mixed to obtain the composite material.
Test example 1 adhesion Performance test
(1) Test samples:
sample 1: blending silk fibroin solution with the concentration of 2.5 wt% and polyphosphoric acid solution with the concentration of 3 wt% according to the mass ratio of polyphosphoric acid to silk fibroin of 1.5:1 to obtain a sample 1;
sample 2: blending silk fibroin solution with the concentration of 2.5 wt% and phytic acid solution with the concentration of 3 wt% according to the mass ratio of phytic acid to silk fibroin of 0.7:1 to obtain a sample 2;
sample 3: blending a soybean protein solution with the concentration of 3 wt% and a polyphosphoric acid solution with the concentration of 3 wt% according to the mass ratio of polyphosphoric acid to soybean protein of 0.6:1 to obtain a sample 3;
sample 4: blending a collagen solution with the concentration of 3 wt% and a polyphosphoric acid solution with the concentration of 3 wt% according to the mass ratio of polyphosphoric acid to collagen of 0.8:1 to obtain a sample 4;
sample 5: blending a bovine serum albumin solution with the concentration of 3 wt% and a polyphosphoric acid solution with the concentration of 3 wt% according to the mass ratio of polyphosphoric acid to bovine serum albumin of 1:1 to obtain a sample 5;
PVDF binder: 0.02g of PVDF is taken and dissolved by 0.2g of N-methyl pyrrolidone to prepare a solution, thus obtaining the PVDF binder.
(2) The test method comprises the following steps:
the adhesive strength of the adhesive was reacted by testing the peel strength of the aluminum foil sheet with the aid of an universal tensile machine. The test method comprises the following steps: taking out two aluminum foil sheets with the specification of 40mm wide and 100mm long, and cleaning the aluminum foil sheets by alcohol before use; during testing, one end of two pieces of aluminum foil is coated with enough adhesive, the coating area is 5.5cm multiplied by 1.3cm, and the aluminum foil is placed in a 60 ℃ oven for 2 hours for drying after being coated; and finally, fixing one end of the stripped sample on a tension probe, stripping at 180 degrees at a constant speed of 10mm/min, and testing the stripping force in the stripping process to represent the strength of the adhesive force of the adhesive.
(3) And (3) test results: see table 1.
Table 1 adhesive Performance test results of the adhesive
Sample (I) Adhesive force (N)
Sample 1 3.22
Sample 2 2.91
Sample 3 3.05
Sample No. 4 2.84
Sample No. 5 2.64
PVDF binder 0.17
As can be seen from the results in table 1, the adhesion of the PVDF binder was only 0.17N, whereas the adhesion of the binder of example 2 of the present invention (sample 1) was 3.22N, which is about 19 times higher than that of the PVDF binder, and the adhesion of the binders of other examples of the present invention was also significantly higher than that of the PVDF binder. The adhesive provided by the invention has more excellent adhesive property, and on one hand, the contact impedance among the active substance, the conductive agent and the adhesive can be reduced, and the utilization rate of the active substance is improved; on the other hand, the structure stability in the electrode circulation process is kept, and the circulation stability of the battery is further improved.
Experimental example 2 visual test of polysulfide adsorption
The test samples were the same as in test example 1.
The test method comprises the following steps: adding ethylene glycol dimethyl ether (DME) into the mixture according to the molar ratio of 1: 3 Li2S and the simple substance S are stirred for 12 hours at room temperature, and then the bright yellow polysulfide Li can be prepared2S4A solution; 20mg of binder sample was weighed and added to 2mL of Li, respectively2S4In the solution, the color change of the solution was observed after standing for 12 hours.
And (3) test results: after the PVDF binder is added, the color of the electrolyte is lightened but still bright yellow, and after the electrostatic combination type aqueous binder provided by the invention is added, the color of the electrolyte is changed into light yellow. The result shows that the electrostatic binding type aqueous binder provided by the invention has better adsorption effect on the polysulfide intermediate product, is beneficial to inhibiting the shuttle effect of the polysulfide, and further improves the cycle stability and the coulombic efficiency of the battery.
Comparative example 1 preparation of lithium-sulfur battery
The method comprises the following steps:
(1) preparation of a sulfur positive electrode: mixing 0.02g of PVDF with 0.12g of sulfur powder and 0.06g of conductive agent Super P, carrying out ball milling in 0.2g of N-methylpyrrolidone to prepare electrode slurry, uniformly coating the electrode slurry on a current collector aluminum foil by adopting a blade coating method, then placing the current collector aluminum foil on a 60 ℃ drying oven for drying for 48 hours, and finally cutting out a pole piece with a corresponding size by using a cutting machine to obtain a sulfur positive pole;
(2) assembling the lithium-sulfur battery: transferring the sulfur positive pole piece prepared in the step (1) into a glove box filled with argon and having water content less than 10ppm, weighing piece by piece, recording, and assembling the sulfur positive pole piece, a polypropylene diaphragm, electrolyte and a lithium negative pole into a battery in the glove box to obtain a lithium-sulfur battery; wherein, 1.0mol/L of lithium bistrifluoromethylsulfonyl imide and 1.0% of lithium nitrate are dissolved in 1, 2-dimethoxyethane and 1, 3-dioxolane 1:1 the mixed solution is used as an electrolyte.
The lithium sulfur battery prepared in comparative example 1 was subjected to an electrical property test by the following method: the test is carried out on a Land2001A battery tester in a constant current charging and discharging mode, the cut-off voltage is 1.7-2.8V, the test current is 0.5C (836mA/g), the test temperature is 30 ℃, and the cycle number is 200.
The test results are: the initial discharge specific capacity of the lithium-sulfur battery assembled by adopting the PVDF binder is only 1000mAh/g under the current density of 0.5C, after 200 cycles, the specific capacity is only 643mAh/g, and the capacity retention rate is 64.3%.
EXAMPLE 7 preparation of lithium-Sulfur Battery
The method comprises the following steps:
(1) dissolving 0.3g of polyphosphoric acid in 10mL of deionized water to prepare polyphosphoric acid solution;
(2) mixing 0.41g of polyphosphoric acid solution (with polyphosphoric acid content of 0.012g), 0.32g of silk fibroin solution (with fibroin protein content of 0.008g) with concentration of 2.5 wt%, 0.12g of sulfur powder and 0.06g of conductive agent Super P, performing ball milling in 0.2g of deionized water to prepare electrode slurry, uniformly coating the electrode slurry on a current collector aluminum foil by adopting a blade coating method, then placing the current collector aluminum foil on a 60 ℃ oven for drying for 48 hours, and finally cutting a pole piece with a corresponding size by using a cutting machine to obtain a sulfur anode;
(3) transferring the sulfur positive pole piece prepared in the step (2) into a glove box filled with argon and having water content less than 10ppm, weighing piece by piece, recording, and assembling the sulfur positive pole piece, the polypropylene diaphragm, the electrolyte and the lithium negative pole together into a battery in the glove box to obtain the lithium-sulfur battery; wherein, 1.0mol/L of lithium bistrifluoromethylsulfonyl imide and 1.0% of lithium nitrate are dissolved in 1, 2-dimethoxyethane and 1, 3-dioxolane 1:1 the mixed solution is used as an electrolyte.
The sulfur positive electrode piece prepared in this example has no crack, and the electrical performance of the prepared lithium-sulfur battery is tested by the same test method as in comparative example 1, and the test result is:
the lithium-sulfur battery of the embodiment is charged and discharged at a rate of 0.5C, the initial specific capacity is 1106mAh/g, the capacity after 200 cycles is still 813mAh/g, the capacity retention rate is 73.5%, and the lithium-sulfur battery shows stable electrochemical performance. Compared with the lithium-sulfur battery assembled by adopting the PVDF binder in the comparative example 1, the lithium-sulfur battery assembled by adopting the electrostatic bonding type aqueous binder provided by the invention has lower initial interface impedance, lower amplification of the interface impedance after circulation and more excellent interface stability.
EXAMPLE 8 preparation of lithium Sulfur Battery
The method comprises the following steps:
(1) dissolving 0.6g of phytic acid in 20mL of deionized water to prepare a phytic acid solution;
(2) mixing 0.57g of phytic acid solution (the phytic acid content is 0.017g), 0.91g of 2.5 wt% silk fibroin solution (the silk fibroin content is 0.023g), 0.24g of sulfur powder and 0.12g of conductive agent Super P, performing ball milling in 0.4g of deionized water to prepare electrode slurry, uniformly coating the electrode slurry on a current collector aluminum foil by adopting a blade coating method, then placing the current collector aluminum foil in a 60 ℃ oven for drying for 48 hours, and finally cutting a pole piece with a corresponding size by using a cutting machine to obtain a sulfur anode;
(3) transferring the sulfur positive pole piece prepared in the step (2) into a glove box filled with argon and having water content less than 10ppm, weighing piece by piece, recording, and assembling the sulfur positive pole piece, the polypropylene diaphragm, the electrolyte and the lithium negative pole together into a battery in the glove box to obtain the lithium-sulfur battery; wherein, 1.0mol/L of lithium bistrifluoromethylsulfonyl imide and 1.0% of lithium nitrate are dissolved in 1, 2-dimethoxyethane and 1, 3-dioxolane 1:1 the mixed solution is used as an electrolyte.
The sulfur positive electrode piece prepared in this example has no crack, and the electrical performance of the prepared lithium-sulfur battery is tested by the same test method as in comparative example 1, and the test result is:
the lithium-sulfur battery of the embodiment is charged and discharged at a multiplying power of 0.5C, the initial specific capacity is 1108mAh/g, the capacity after 200 cycles is still maintained at 806mAh/g, and the capacity retention rate is 72.74%. And compared with the lithium-sulfur battery assembled by adopting the PVDF binder in the comparative example 1, the lithium-sulfur battery assembled by the embodiment has lower initial interface resistance and lower increase of the interface resistance after the circulation.
EXAMPLE 9 preparation of lithium Sulfur Battery
The method comprises the following steps:
(1) dissolving 0.3g of polyphosphoric acid in 10mL of deionized water to prepare polyphosphoric acid solution;
(2) mixing 0.29g of polyphosphoric acid solution (with polyphosphoric acid content of 0.008g), 0.43g of soybean protein solution with concentration of 3 wt% (with soybean protein content of 0.013g), 0.14g of sulfur powder and 0.07g of conductive agent Super P, performing ball milling in 0.3g of deionized water to prepare electrode slurry, uniformly coating the electrode slurry on a current collector aluminum foil by adopting a blade coating method, then placing the current collector aluminum foil in a 60 ℃ oven for drying for 48 hours, and finally cutting a pole piece with a corresponding size by using a cutting machine to obtain a sulfur positive pole;
(3) transferring the sulfur positive pole piece prepared in the step (2) into a glove box filled with argon and having water content less than 10ppm, weighing piece by piece, recording, and assembling the sulfur positive pole piece, the polypropylene diaphragm, the electrolyte and the lithium negative pole together into a battery in the glove box to obtain the lithium-sulfur battery; wherein, 1.0mol/L of lithium bistrifluoromethylsulfonyl imide and 1.0% of lithium nitrate are dissolved in 1, 2-dimethoxyethane and 1, 3-dioxolane 1:1 the mixed solution is used as an electrolyte.
The sulfur positive electrode piece prepared in this example has no crack, and the electrical performance of the prepared lithium-sulfur battery is tested by the same test method as in comparative example 1, and the test result is:
the lithium-sulfur battery of the embodiment is charged and discharged at a multiplying power of 0.5C, the initial specific capacity is 1120mAh/g, the capacity after 200 cycles is still kept at 795mAh/g, and the capacity retention rate is 70.98%. And the assembled lithium-sulfur battery of the present example had a lower initial interfacial resistance and a lower increase in interfacial resistance after cycling, compared to the lithium-sulfur battery of comparative example 1.
EXAMPLE 10 preparation of lithium Sulfur Battery
The method comprises the following steps:
(1) dissolving 0.3g of polyphosphoric acid in 10mL of deionized water to prepare polyphosphoric acid solution;
(2) mixing 0.31g of polyphosphoric acid solution (with the polyphosphoric acid content being 0.009g), 0.37g of collagen solution with the concentration being 3 wt% (with the collagen content being 0.011g), 0.12g of sulfur powder and 0.06g of conductive agent Super P, performing ball milling in 0.4g of deionized water to prepare electrode slurry, uniformly coating the electrode slurry on a current collector aluminum foil by adopting a blade coating method, then placing the current collector aluminum foil in a 60 ℃ oven for drying for 48 hours, and finally cutting a pole piece with a corresponding size by using a cutting machine to obtain a sulfur positive pole;
(3) transferring the sulfur positive pole piece prepared in the step (2) into a glove box filled with argon and having water content less than 10ppm, weighing piece by piece, recording, and assembling the sulfur positive pole piece, the polypropylene diaphragm, the electrolyte and the lithium negative pole together into a battery in the glove box to obtain the lithium-sulfur battery; wherein, 1.0mol/L of lithium bistrifluoromethylsulfonyl imide and 1.0% of lithium nitrate are dissolved in 1, 2-dimethoxyethane and 1, 3-dioxolane 1:1 the mixed solution is used as an electrolyte.
The sulfur positive electrode piece prepared in this example has no crack, and the electrical performance of the prepared lithium-sulfur battery is tested by the same test method as in comparative example 1, and the test result is:
the lithium-sulfur battery of the embodiment is charged and discharged at a multiplying power of 0.5C, the initial specific capacity is 1131mAh/g, the capacity after 200 cycles is still 786mAh/g, and the capacity retention rate is 69.56%. And the assembled lithium-sulfur battery of the present example had a lower initial interfacial resistance and a lower increase in interfacial resistance after cycling, compared to the lithium-sulfur battery of comparative example 1.
EXAMPLE 11 preparation of lithium Sulfur Battery
The method comprises the following steps:
(1) dissolving 0.3g of polyphosphoric acid in 10mL of deionized water to prepare polyphosphoric acid solution;
(2) mixing 0.43g of polyphosphoric acid solution (with polyphosphoric acid content of 0.013g), 0.43g of bovine serum albumin solution with concentration of 3 wt% (with bovine serum albumin content of 0.013g), 0.16g of sulfur powder and 0.08g of conductive agent Super P, performing ball milling in 0.4g of deionized water to prepare electrode slurry, uniformly coating the electrode slurry on a current collector aluminum foil by adopting a blade coating method, then placing the current collector aluminum foil in a 60 ℃ oven for drying for 48 hours, and finally cutting a pole piece with a corresponding size by using a cutting machine to obtain a sulfur positive pole;
(3) transferring the sulfur positive pole piece prepared in the step (2) into a glove box filled with argon and having water content less than 10ppm, weighing piece by piece, recording, and assembling the sulfur positive pole piece, the polypropylene diaphragm, the electrolyte and the lithium negative pole together into a battery in the glove box to obtain the lithium-sulfur battery; wherein, 1.0mol/L of lithium bistrifluoromethylsulfonyl imide and 1.0% of lithium nitrate are dissolved in 1, 2-dimethoxyethane and 1, 3-dioxolane 1:1 the mixed solution is used as an electrolyte.
The sulfur positive electrode piece prepared in this example has no crack, and the electrical performance of the prepared lithium-sulfur battery is tested by the same test method as in comparative example 1, and the test result is:
the lithium-sulfur battery of the embodiment is charged and discharged at a multiplying power of 0.5C, the initial specific capacity is 1094mAh/g, the capacity after 200 cycles is still kept at 796mAh/g, and the capacity retention rate is 72.76%. And the assembled lithium-sulfur battery of the present example had a lower initial interfacial resistance and a lower increase in interfacial resistance after cycling, compared to the lithium-sulfur battery of comparative example 1.
What has been described above are merely some embodiments of the present invention. It will be apparent to those skilled in the art that various changes and modifications can be made without departing from the inventive concept thereof, and these changes and modifications can be made without departing from the spirit and scope of the invention.

Claims (9)

1. An electrostatically binding aqueous binder consisting of a component a and a component B which are present independently, wherein:
the component A is a compound containing a phosphate group and/or a compound solution containing a phosphate group; the concentration of the compound solution containing phosphoric acid groups is 1-10 wt%;
the component B is a compound containing an amino group and/or a compound solution containing an amino group; the concentration of the compound solution containing amino groups is 1-10 wt%;
when the phosphate-group-containing compound is used, the component A and the component B are mixed according to the mass ratio of the phosphate-group-containing compound to the amino-group-containing compound of 0.5:1-2:1, and when the component A and/or the component B are compounds, the compounds are prepared into a solution with the concentration of 1-10wt% and then mixed;
wherein the compound containing phosphate groups is selected from one or two of polyphosphoric acid and phytic acid; the compound containing amino groups is at least one selected from silk fibroin, collagen, soybean protein and bovine serum albumin.
2. The electrostatically binding aqueous binder as claimed in claim 1, wherein the phosphoric acid group-containing compound is polyphosphoric acid, and the amino group-containing compound is silk fibroin.
3. The method for preparing an electrostatically binding aqueous binder according to claim 2, comprising the steps of:
(1) adding silkworm cocoon into sodium carbonate solution with concentration of 4-10g/L according to solid-to-liquid ratio of 10-50g/L, heating to 80-100 deg.C, maintaining for 1-2 hr, filtering, and drying the filter residue to obtain fibroin;
(2) adding silk fibroin into 7-10M lithium bromide solution, dissolving, filtering with filter cloth, and dialyzing with dialysis membrane with molecular weight cutoff of 3.5-10kDa to obtain 1-10wt% silk fibroin solution;
(3) taking polyphosphoric acid, and independently packaging the polyphosphoric acid and the silk fibroin solution to obtain an electrostatic binding type aqueous binder, wherein the polyphosphoric acid is taken according to the mass ratio of the polyphosphoric acid to the silk fibroin of 0.5:1-2:1 when the electrostatic binding type aqueous binder is used, then the polyphosphoric acid is added with water to prepare a polyphosphoric acid solution with the concentration of 1-10wt%, and the polyphosphoric acid solution is mixed with the silk fibroin solution; or
Taking polyphosphoric acid, adding water to prepare 1-10wt% polyphosphoric acid solution, and separately packaging with silk fibroin solution to obtain electrostatic binding type aqueous binder, wherein the polyphosphoric acid solution and the silk fibroin solution are mixed according to the mass ratio of polyphosphoric acid to silk fibroin of 0.5:1-2: 1.
4. Use of the electrostatically bound aqueous binder according to any one of claims 1 to 2 for the preparation of an electrode for a lithium ion battery.
5. The use of claim 4, wherein the electrode is one of a sulfur positive electrode, a lithium cobaltate positive electrode, a lithium iron phosphate positive electrode, a lithium cobalt manganese ternary positive electrode, a silicon-based negative electrode, or a graphite-based negative electrode.
6. The sulfur positive electrode of the lithium-sulfur battery comprises a current collector and a positive electrode material coated on the current collector, wherein the positive electrode material comprises the following components in parts by weight: 6-8 parts of active material, 1-4 parts of conductive agent and 0.5-1.5 parts of binder in parts by weight calculated by solid content, wherein the binder is the electrostatic combination type water-based binder in any one of claims 1-2.
7. The sulfur positive electrode of claim 6, wherein the active material is selected from sublimed sulfur, Li2S2、Li2S4、Li2S6、Li2S8At least one of; the conductive agent is at least one of acetylene black, conductive graphite, Super P, Ketjen black and carbon nano tubes; the current collector is selected from one of copper foil, aluminum foil, copper foam, non-woven fabric plated with copper, nickel foam and non-woven fabric plated with nickel.
8. The method for producing a sulfur positive electrode according to claim 6 or 7, comprising the steps of:
(1) ball-milling and mixing a compound solution containing a phosphate group, a compound solution containing an amino group, an active material and a conductive agent to obtain electrode slurry;
(2) and coating the electrode slurry on a current collector, drying, and then preparing a pole piece to obtain the sulfur positive electrode.
9. A lithium-sulfur battery comprising the sulfur positive electrode according to claim 6 or 7.
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CN105860922A (en) * 2016-05-09 2016-08-17 北京林业大学 Bean pulp-base artificial board adhesive and preparation method thereof

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