CN115036508A - Lithium-sulfur battery positive electrode material, lithium-sulfur battery positive electrode plate and lithium-sulfur battery - Google Patents
Lithium-sulfur battery positive electrode material, lithium-sulfur battery positive electrode plate and lithium-sulfur battery Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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
- H01M4/13—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
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- 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
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Abstract
The invention provides a lithium-sulfur battery positive electrode material, a lithium-sulfur battery positive electrode plate and a lithium-sulfur battery. The lithium-sulfur battery positive electrode material comprises a positive electrode active substance, a binder and a conductive agent, wherein the binder is a modified polyacrylamide binder, and the modified polyacrylamide binder comprises modified polyacrylamide shown as a structural formula I:
wherein R is 1 Is an unsaturated acid group, R 2 Is a hydroxyl-containing group. The existence of the modified polyacrylamide binder is beneficial to adsorbing polysulfide generated in the charge and discharge process of the battery and inhibiting polysulfideThe high adhesion of the modified polyacrylamide adhesive can avoid phenomena of pole piece powder falling, stripping, active substance falling and the like to a great extent, and inhibit volume expansion, shrinkage and stress change of the anode material in the battery circulation process.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to a lithium-sulfur battery positive electrode material, a lithium-sulfur battery positive electrode plate and a lithium-sulfur battery.
Background
The problems of environmental pollution, greenhouse effect, energy crisis and the like in the world are increasingly serious. The secondary battery having high specific energy has very important significance for solving energy and environmental problems. Among them, the lithium ion battery is one of the batteries having the highest specific energy among the secondary batteries. However, in the lithium ion battery system, the specific capacity and the cycle performance of the positive electrode material need to be further optimized. The lithium-sulfur battery is a kind of lithium battery, and the lithium-sulfur battery is a kind of lithium battery with elemental sulfur as the positive electrode of the battery and metallic lithium as the negative electrode. The lithium-sulfur battery using sulfur as the anode material has a theoretical specific capacity of 1675mAh/g, a theoretical specific energy of 2600Wh/kg, and is LiCoO 2 Graphite and LiFePO 4/ Graphite systems are 6 times more than commercial secondary batteries used at the present stage. In addition, the elemental sulfur has abundant reserves in the earth, and has the advantages of low cost, environmental friendliness and the like with extremely high commercial value.
However, the lithium sulfur battery has the following problems in moving to commercialization: (1) lithium polysulfide (Li) as intermediate product generated during charging and discharging of lithium-sulfur battery 2 S x X is more than or equal to 4 and less than or equal to 8) is easily dissolved in the organic electrolyte, so that the active substances on the positive electrode are gradually reduced, and the dissolved lithium polysulfide can penetrate through the diaphragm and diffuse to the negative electrode lithium plate of the battery due to the shuttle effect, and the generated Li 2 S 2 And Li 2 S precipitate has poor conductivity, causing corrosion of the negative electrode of the battery and increase of the internal resistance of the battery, and the shuttle effect also causes Li 2 S 2 And Li 2 S deposits on the surface of the positive electrode, resulting in a significant change in the electrode morphology, which in turn results in a rapid decay in capacity. (2) During cycling, the volume expansion of the sulfur electrode in a lithium sulfur battery is as high as 80%, which can cause cracks to form inside the sulfur electrode, the presence of such cracks and Li 2 S 2 And Li 2 The formation of S at the crack destroys the integrity of the positive electrode, eventually leading to a rapid decay of capacity. Due to the above problemsIn the process of charging and discharging, the lithium-sulfur battery has the phenomena of low specific discharge capacity and poor cycling stability. To solve the above problems, the preparation of a sulfur positive electrode material having excellent electrochemical properties is one of important solutions. The binder is used as an important part of the cathode material and plays a key role in preparing the lithium-sulfur battery with excellent electrochemical performance.
Therefore, there is an urgent need to develop a positive electrode material for a lithium-sulfur battery, a positive electrode sheet for a lithium-sulfur battery, and a lithium-sulfur battery, so that the lithium-sulfur battery can improve the utilization rate of active material sulfur, limit the dissolution of lithium polysulfide, and improve cycle stability.
Disclosure of Invention
The invention aims to provide a lithium-sulfur battery positive electrode material, a lithium-sulfur battery positive electrode sheet and a lithium-sulfur battery, so that the lithium-sulfur battery can improve the utilization rate of active substance sulfur, limit the dissolution of lithium polysulfide and improve the cycling stability of the battery.
In order to achieve the above object, the present invention provides a positive electrode material for a lithium-sulfur battery, including a positive electrode active material, a binder and a conductive agent, wherein the binder is a modified polyacrylamide binder, and the modified polyacrylamide binder includes a modified polyacrylamide represented by structural formula i:
wherein R is 1 Is an unsaturated acid group, R 2 Is a hydroxyl-containing group.
Preferably, the unsaturated acid group is selected from one or more of unsaturated carboxylic acid, unsaturated sulfonic acid and unsaturated phosphoric acid.
Preferably, the unsaturated carboxylic acid is one or more selected from the group consisting of acrylic acid (CAS number: 79-10-7), methacrylic acid (CAS number: 79-41-4), crotonic acid (CAS number: 107-93-7), maleic acid (CAS number: 110-16-7), fumaric acid (CAS number: 110-17-8), and itaconic acid (CAS number: 97-65-4).
The unsaturated sulfonic acid is one or more selected from tert-butyl acrylamide sulfonic acid (CAS number: 15214-89-8), trimethylolpropane trimethacrylate (CAS number: 3290-92-4) and styrene sulfonic acid.
The unsaturated phosphoric acid is selected from one or more of vinyl phosphoric acid (CAS No: 1746-03-8), bis [2- (methacryloyloxy) ethyl ] phosphate (CAS No: 32435-46-4) and bis [2- (acryloyloxy) ethyl ] phosphate (CAS No: 40074-34-8).
Preferably, the binder is configured into a glue solution with 13.0-14.0% of the binder by mass, and the pH value of the glue solution is 2.0-4.0.
Preferably, the positive active material is selected from one or more of elemental sulfur, sulfide, and sulfur-containing compound.
Preferably, the conductive agent is selected from one or more of carbon black, graphene, carbon nanotubes, acetylene black and conductive graphite.
Preferably, the mass part ratio of the positive electrode active material to the conductive agent to the binder is 1-10: 1-10: 1 to 5.
The invention also provides a lithium-sulfur battery positive plate which comprises a current collector and the lithium-sulfur battery positive material, wherein the lithium-sulfur battery positive material is coated on the current collector.
Preferably, the loading capacity of the positive electrode material of the lithium-sulfur battery on the current collector is 0.5-10 mg/cm -2 。
The invention also provides a lithium-sulfur battery, which comprises a negative plate, electrolyte, a diaphragm and the positive plate of the lithium-sulfur battery.
Compared with the prior art, the modified polyacrylamide binder in the lithium-sulfur battery positive electrode material contains a large number of amide groups and hydroxyl groups, which are beneficial to adsorbing polysulfide with negative charges generated in the lithium-sulfur battery charging and discharging process, the acidic groups contained in the binder enable the sulfur-containing positive electrode material to form an acidic microenvironment, and when the polysulfide is formed by sulfur and lithium in the lithium-sulfur battery discharging process, due to the existence of the local acidic microenvironment, the polysulfide is subjected to disproportionation reaction and can generate elemental sulfur in situ, so that the dissolution of the polysulfide in electrolyte is inhibited, the utilization efficiency of sulfur elements is improved, and the discharge capacity of the lithium-sulfur battery is improved. Meanwhile, due to the high adhesion of the polyacrylamide adhesive, the positive active substance and the conductive agent are uniformly dispersed and firmly adhered on the current collector, so that the phenomena of pole piece powder falling, stripping, active substance falling and the like are avoided to a great extent. The binder generates a cross-linking reaction in the manufacturing process of the pole piece to inhibit the volume expansion and contraction and stress change of the positive pole material in the battery cycle process, and the cycle characteristic of the lithium-sulfur battery is improved.
Drawings
FIG. 1 Electron micrograph of Positive electrode sheet prepared with PVDF as Binder and Positive electrode sheet prepared with Binder in example 1
aPVDF
b acrylamide-styrene sulfonic acid-allyl alcohol copolymer
Fig. 2 is a graph showing rate performance test of a lithium sulfur battery assembled with a positive electrode sheet for a lithium sulfur battery prepared according to examples and comparative examples as a positive electrode for a lithium sulfur battery.
FIG. 3 is a graph of the absorption spectra of polysulfide UV-vis for the binders in the examples and the binders in the comparative examples.
Fig. 4 is a graph showing cycle performance tests of lithium sulfur batteries assembled with positive electrode sheets of lithium sulfur batteries prepared according to examples and comparative examples as positive electrodes.
Fig. 5 is a comparison graph of ac impedance before and after cycles of a lithium sulfur battery assembled with a positive electrode sheet of the lithium sulfur battery prepared according to the example and the comparative example as a positive electrode.
Detailed Description
The following examples are given for the purpose of illustrating the technical content of the present invention in detail, but are not to be construed as limiting the present invention.
First, the components and contents of the positive electrode material for lithium-sulfur batteries, and the methods of preparing the positive electrode sheet for lithium-sulfur batteries and the lithium-sulfur battery in example 1 are as follows.
The positive electrode material of the lithium-sulfur battery comprises, by mass, 14 parts of a positive electrode active substance, 4 parts of a conductive agent and 2 parts of a modified polyacrylamide binder. The anode active substance is selected from elemental sulfur, the conductive agent is selected from carbon black (SuperP), and the modified polyacrylamide binder is acrylamide-styrene sulfonic acid-allyl alcohol copolymer.
The preparation method of the acrylamide-styrene sulfonic acid-allyl alcohol copolymer comprises the following steps: mixing acrylamide, styrene sulfonic acid and allyl alcohol, reacting for 1-6 hours at 45-65 ℃ under normal pressure, adding urea as a reaction auxiliary agent, inhibiting product crosslinking, and weakening the hydrogen bond association effect of polymer molecules. After the copolymer is formed, sodium hydroxide is added, an ionizable group is introduced to enable the polymer chain of the copolymer to be easily separated, and meanwhile, a surfactant, namely nonylphenol polyoxyethylene ether, is added to accelerate the dissolution speed. Then, the copolymer is transferred to a roller press to be pressed into slices, and acrylamide-styrene sulfonic acid-allyl alcohol copolymer solid powder is prepared after dehydration, drying, crushing and sieving.
The preparation method of the positive plate of the lithium-sulfur battery comprises the following steps:
(1) dissolving a modified polyacrylamide binder and deionized water into the deionized water to prepare a glue solution with the binder mass fraction of 13.0-14.0%, wherein the pH value of the glue solution is 2.0-4.0;
(2) adding an anode active substance into the glue solution, adding a proper amount of conductive agent, uniformly stirring, and performing ultrasonic treatment at room temperature for 40min to obtain an anode mixed solution;
(3) and performing ball milling on the positive electrode mixed solution to obtain slurry, uniformly coating the slurry on a current collector, and controlling the loading capacity of the positive electrode material of the lithium-sulfur battery on the current collector to be 2mg -2 And (3) drying the coating in a drying oven at the coating temperature of 25 ℃ for 12h and the temperature of 60 ℃, and drying in a vacuum drying oven for 12h at the relative vacuum degree of less than-0.1 MPa and the temperature of 60 ℃ to obtain the lithium-sulfur battery positive plate.
The preparation method of the lithium-sulfur battery comprises the following steps: the button cell is assembled according to the sequence of 'negative electrode shell-lithium sheet-electrolyte-diaphragm-electrolyte-positive electrode sheet-positive electrode shell', the battery specification is 2025, the whole process is completed in a glove box filled with argon, wherein the electrolyte is (0.6M LITFSiDOL/DME), the diaphragm is Celgard2400, and the performance of the assembled battery is tested by using a blue battery tester.
Secondly, the components and contents of the lithium-sulfur battery positive electrode material in example 2, and the preparation methods of the lithium-sulfur battery positive electrode sheet and the lithium-sulfur battery are as follows.
The positive electrode material of the lithium-sulfur battery comprises, by mass, 14 parts of a positive electrode active substance, 2 parts of a conductive agent and 4 parts of a modified polyacrylamide binder. The anode active substance is elemental sulfur, the conductive agent is 1.8 parts of carbon black (SuperP) and 0.2 part of single-walled carbon nanotube, and the modified polyacrylamide binder is acrylamide-acrylic acid-allyl alcohol copolymer.
The preparation method of the acrylamide-acrylic acid-allyl alcohol copolymer comprises the following steps: mixing acrylamide, acrylic acid and allyl alcohol, reacting for 1-6 hours at 45-65 ℃ under normal pressure, adding urea as a reaction auxiliary agent, inhibiting product crosslinking, and weakening the hydrogen bond association effect of polymer molecules. After the copolymer is formed, sodium hydroxide is added, an ionizable group is introduced to enable the polymer chain of the copolymer to be easily separated, and meanwhile, a surfactant, namely nonylphenol polyoxyethylene ether, is added to accelerate the dissolution speed. Then, the copolymer is transferred to a roller press to be pressed into slices, and the acrylamide-acrylic acid-allyl alcohol copolymer solid powder is prepared after dehydration, drying, crushing and sieving.
The preparation method of the positive plate of the lithium-sulfur battery comprises the following steps:
(1) dissolving a modified polyacrylamide binder and deionized water into the deionized water to prepare a glue solution with the binder mass fraction of 13.0-14.0%, wherein the pH value of the glue solution is 2.0-4.0;
(2) adding the positive active substance into the glue solution, adding a proper amount of conductive agent, uniformly stirring, and performing ultrasonic treatment at room temperature for 40min to obtain a positive mixed solution;
(3) and performing ball milling on the positive electrode mixed solution to obtain slurry, uniformly coating the slurry on a current collector, and controlling the loading capacity of the positive electrode material of the lithium-sulfur battery on the current collector to be 2mg -2 And the coating temperature is 25 ℃, then the obtained product is put into a drying oven for drying for 12 hours at the temperature of 60 ℃, and then the obtained product is put into a vacuum drying oven for drying for 12 hours at the relative vacuum degree of less than-0.1 MPa and the temperature of 60 ℃ to obtain the lithium-sulfur battery positive plate.
The preparation method of the lithium-sulfur battery comprises the following steps: the button cell is assembled according to the sequence of 'negative electrode shell-lithium sheet-electrolyte-diaphragm-electrolyte-positive electrode sheet-positive electrode shell', the battery specification is 2025, the whole process is completed in a glove box filled with argon, wherein the electrolyte is (0.6M LITFSI DOL/DME), the diaphragm is Celgard2400, and the performance of the assembled battery is tested by using a blue battery tester.
And thirdly, the components and the content of the lithium-sulfur battery positive electrode material in the comparative example 1, and the preparation methods of the lithium-sulfur battery positive electrode sheet and the lithium-sulfur battery are as follows.
The positive electrode material of the lithium-sulfur battery comprises, by mass, 14 parts of a positive electrode active material, 4 parts of a conductive agent and 2 parts of a binder. The positive active substance is elemental sulfur, the conductive agent is carbon black (SuperP), and the binder is polyvinylidene fluoride (PVDF) (oily binder).
The preparation method of the lithium-sulfur battery positive plate comprises the following steps:
(1) dissolving PVDF in NMP to prepare a glue solution with 13.0-14.0% of binder mass fraction by taking PVDF as a binder and N-methylpyrrolidone (NMP) as a solvent;
(2) adding an anode active substance into the glue solution, adding a proper amount of conductive agent, uniformly stirring, and performing ultrasonic treatment at room temperature for 40min to obtain an anode mixed solution;
(3) ball-milling the positive electrode mixed solution to obtain slurry, uniformly coating the slurry on a current collector, and controlling the loading capacity of the positive electrode material of the lithium-sulfur battery in the current collector to be 2mg -2 And the coating temperature is 25 ℃, then the obtained product is put into a drying oven for drying for 12 hours at the temperature of 60 ℃, and then the obtained product is put into a vacuum drying oven for drying for 12 hours at the relative vacuum degree of less than-0.1 MPa and the temperature of 60 ℃ to obtain the lithium-sulfur battery positive plate.
The preparation method of the lithium-sulfur battery comprises the following steps: the button cell is assembled according to the sequence of 'negative electrode shell-lithium sheet-electrolyte-diaphragm-electrolyte-positive electrode sheet-positive electrode shell', the specification of the cell is 2025, the whole process is completed in a glove box filled with argon, wherein the electrolyte is (0.6M LITFSI DOL/DME), the diaphragm is Celgard2400, and the performance of the assembled cell is tested by a blue tester.
Fourthly, the components and contents of the positive electrode material for the lithium-sulfur battery in comparative example 2, and the methods of preparing the positive electrode sheet for the lithium-sulfur battery and the lithium-sulfur battery are as follows.
The positive electrode material of the lithium-sulfur battery comprises, by mass, 14 parts of a positive electrode active material, 4 parts of a conductive agent and 2 parts of a binder. The anode active substance is elemental sulfur, the conductive agent is carbon black (SuperP), and the binder is polyacrylic acid PAA (water-based binder).
The preparation method of the positive plate of the lithium-sulfur battery comprises the following steps:
(1) dissolving PAA in NMP to prepare a glue solution with 13.0-14.0% of binder mass fraction, wherein the binder PAA and a solvent N-methylpyrrolidone (NMP) are taken;
(2) adding the positive active substance into the glue solution, adding a proper amount of conductive agent, uniformly stirring, and performing ultrasonic treatment at room temperature for 40min to obtain a positive mixed solution;
(3) ball-milling the positive electrode mixed solution to obtain slurry, uniformly coating the slurry on a current collector, and controlling the loading capacity of the positive electrode material of the lithium-sulfur battery at the current collector to be 2mg 2 And the coating temperature is 25 ℃, then the obtained product is put into a drying oven for drying for 12 hours at the temperature of 60 ℃, and then the obtained product is put into a vacuum drying oven for drying for 12 hours at the relative vacuum degree of less than-0.1 MPa and the temperature of 60 ℃ to obtain the lithium-sulfur battery positive plate.
The preparation method of the lithium-sulfur battery comprises the following steps: the button cell is assembled according to the sequence of 'negative electrode shell-lithium sheet-electrolyte-diaphragm-electrolyte-positive electrode sheet-positive electrode shell', the specification of the cell is 2025, the whole process is completed in a glove box filled with argon, wherein the electrolyte is (0.6M LITFSI DOL/DME), the diaphragm is Celgard2400, and the performance of the assembled cell is tested by a blue tester.
Further examination was made on the lithium sulfur batteries prepared according to examples 1 and 2 and comparative examples 1 and 2 described above.
1. Rate capability test
The prepared button cell is tested on a blue cell tester, the voltage range of the test is 1.7V-2.8V, the current density is 0.1C (1C is 1675mA/mg) for the first two times, and the subsequent current density is 1C; the voltage range of the multiplying power performance test is 1.7V-2.8V, the current density is 0.1C, 0.2C, 0.5C, 1C, 2C and 0.5C in sequence, and 5 cycles are respectively carried out when the current density is 0.1C, 0.2C, 0.5C, 1C, 2C and 0.5C. The test results are shown in fig. 2.
2. Testing of adhesive Properties to polysulfide adsorption
Adding ethylene glycol dimethyl ether (DME) into the mixture according to the molar ratio of 1: 3 Li 2 S and simple substance S are stirred for 12 hours at room temperature, and bright yellow polysulfide Li can be prepared 2 S 4 A solution; 20mg of binder was weighed out and added to 2mL of Li 2 S 4 In the solution, after standing for 12h, UV-Vis spectrum test is carried out, and the test result is shown in figure 3.
3. Cycle performance test procedure
The prepared button cell is tested on a blue cell tester, the voltage range of the test is 1.7V-2.8V, and the current density is 1C (1C: 1675 mA/mg); cycle 500 cycles at 1C. The test results are shown in fig. 4.
4. And (3) testing alternating current impedance: the test result is shown in fig. 5 when the test is performed by an ac impedance tester.
5. Lithium-sulfur battery pole piece peel strength test
The peel strength test method of the lithium-sulfur battery positive plate is a tensile tester method known to those skilled in the art, and the test results are shown in table 1.
TABLE 1 Peel Strength of Positive electrode sheet for lithium-sulfur Battery obtained from Positive electrode Material for lithium-sulfur Battery in examples 1 to 2 and comparative examples 1 to 2
| Examples | Positive plate peeling strength (N/mm) |
| Example 1 | 1.15 |
| Example 2 | 1.12 |
| Comparative example 1 | 0.51 |
| Comparative example 2 | 0.22 |
Test results show that the modified polyacrylamide binder in the lithium-sulfur battery cathode material can improve the discharge capacity of the lithium-sulfur battery. Meanwhile, due to the high adhesion of the polyacrylamide adhesive, the positive active substance and the conductive agent are uniformly dispersed and firmly adhered on the current collector, so that the phenomena of pole piece powder falling, stripping, active substance falling and the like are avoided to a great extent. The modified polyacrylamide binder can inhibit the volume expansion and contraction and stress change of the positive electrode material in the battery cycle process, and improve the cycle characteristics of the lithium-sulfur battery.
The above disclosure is only a preferred embodiment of the present invention, and should not be taken as limiting the scope of the invention, so that the appended claims are intended to cover all such modifications and changes as fall within the true spirit of the invention.
Claims (10)
1. The positive electrode material of the lithium-sulfur battery is characterized by comprising a positive electrode active material, a binder and a conductive agent, wherein the binder is a modified polyacrylamide binder, and the modified polyacrylamide binder comprises modified polyacrylamide shown as a structural formula I:
wherein R is 1 Is an unsaturated acid group, R 2 Is a hydroxyl-containing group.
2. The positive electrode material for a lithium-sulfur battery according to claim 1, wherein the unsaturated acid group is one or more selected from the group consisting of unsaturated carboxylic acid, unsaturated sulfonic acid and unsaturated phosphoric acid.
3. The positive electrode material for the lithium-sulfur battery according to claim 2, wherein the unsaturated carboxylic acid is one or more selected from acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid; the unsaturated sulfonic acid is selected from one or more of tert-butyl acrylamide sulfonic acid, trimethylolpropane trimethacrylate and styrene sulfonic acid; the unsaturated phosphoric acid is selected from one or more of vinyl phosphoric acid, bis [2- (methacryloyloxy) ethyl ] phosphate and bis [2- (acryloyloxy) ethyl ] phosphate.
4. The positive electrode material of the lithium-sulfur battery as claimed in claim 1, wherein the binder is configured into a glue solution with a mass fraction of 13.0-14.0%, and the pH value of the glue solution is 2.0-4.0.
5. The positive electrode material for a lithium-sulfur battery according to claim 1, wherein the positive active material is one or more selected from elemental sulfur, a sulfide, and a sulfur-containing compound.
6. The positive electrode material for lithium-sulfur batteries according to claim 1, wherein the conductive agent is one or more selected from carbon black, graphene, carbon nanotubes, acetylene black and conductive graphite.
7. The positive electrode material for the lithium-sulfur battery as defined in claim 1, wherein the mass ratio of the positive electrode active material to the conductive agent to the binder is 1-10: 1-10: 1 to 5.
8. A positive plate of a lithium-sulfur battery, which is characterized by comprising a current collector and the positive material of the lithium-sulfur battery as claimed in any one of claims 1 to 7, wherein the positive material of the lithium-sulfur battery is coated on the current collector.
9. The positive plate of the lithium-sulfur battery as claimed in claim 8, wherein the loading of the positive material of the lithium-sulfur battery on the current collector is 0.5-10 mg/cm -2 。
10. A lithium-sulfur battery comprising a negative electrode sheet, an electrolyte, a separator and the positive electrode sheet according to any one of claims 8 to 9.
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| CN112652773A (en) * | 2020-12-24 | 2021-04-13 | 中山大学 | Multifunctional self-repairing binder for lithium-sulfur battery positive electrode and preparation method and application thereof |
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| CN105870455A (en) * | 2016-06-06 | 2016-08-17 | 北京师范大学 | Sulfur-containing anode acid bonding agent, lithium sulfur battery and preparing method |
| CN110190284A (en) * | 2019-06-25 | 2019-08-30 | 武汉大学 | A kind of lithium-sulphur cell positive electrode water-based binder and its preparation method and application |
| CN111129457A (en) * | 2019-12-19 | 2020-05-08 | 名添科技（深圳）有限公司 | Aqueous ternary cathode slurry and preparation method thereof |
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