CN111540871A - Diaphragm, preparation method thereof and lithium-sulfur battery - Google Patents
Diaphragm, preparation method thereof and lithium-sulfur battery Download PDFInfo
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- CN111540871A CN111540871A CN202010384811.1A CN202010384811A CN111540871A CN 111540871 A CN111540871 A CN 111540871A CN 202010384811 A CN202010384811 A CN 202010384811A CN 111540871 A CN111540871 A CN 111540871A
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
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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
- 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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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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
- Y02E60/10—Energy storage using batteries
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Abstract
The invention provides a diaphragm, which comprises sulfonated siloxane-based graphene aerogel, wherein the sulfonated siloxane-based graphene aerogel comprises graphene oxide, siloxane groups bridging the graphene oxide, and sulfonic acid groups; wherein the siloxane group is
R is C2‑5And linking the sulfonic acid group. Also provided are a method of preparing the separator and a lithium sulfur battery including the separator. The membrane provided by the invention comprises the sulfonated siloxane-based graphene aerogel, has the advantages of high strength and elastic modulus, good interface compatibility with electrolyte, high electronic insulation, good flexibility, easiness in processing, good thermal stability and the like, and can effectively block shuttling of polysulfide and improve electric propertyThe cell performance.
Description
Technical Field
The invention belongs to the field of chemical power sources, and particularly relates to a diaphragm, a preparation method of the diaphragm and a lithium-sulfur battery.
Background
The aerogel is used as a novel material with low density and a porous structure, is not only an excellent electrode material carrier, but also has certain application in a functional diaphragm. The existing aerogel mainly comprises graphene aerogel, organic compound aerogel, inorganic compound aerogel and the like. The graphene aerogel synthesis technology is mature, has the advantages of high elastic modulus, high toughness and porosity, but has poor compatibility with electrolyte, and high conductivity, so that the graphene aerogel is suitable for being used as a coating and cannot be directly used as a diaphragm; the organic aerogel has good flexibility, but has poor mechanical property, is easy to puncture, and has poor heat insulation property; the metal oxide aerogel is brittle in material, low in elastic modulus, not suitable for being directly used as a diaphragm, and harsh in synthesis conditions, and needs to be synthesized by supercritical drying.
Disclosure of Invention
In order to overcome the above-mentioned disadvantages, the present invention provides a sulfonated siloxane-based graphene aerogel separator, a method of preparing the same, and a lithium sulfur battery including the same.
The invention provides a membrane, which comprises sulfonated siloxane-based graphene aerogel, wherein the sulfonated siloxane-based graphene aerogel comprises graphene oxide, siloxane groups bridging the graphene oxide, and sulfonic acid groups;
wherein the siloxane group is
R is C2-5And linking the sulfonic acid group.
In another aspect, the present invention provides a method for preparing a separator, including: preparing a dispersion liquid of graphene oxide; adding a silane coupling agent containing sulfydryl into the dispersion liquid and stirring to form sulfhydrylated graphene hydrogel; and drying the sulfhydrylation graphene hydrogel, placing the dried sulfhydrylation graphene hydrogel in a solution containing an oxidant, and oxidizing sulfhydryl into a sulfonic acid group to obtain the sulfonated siloxane-based graphene hydrogel.
In another aspect, the present invention also provides a lithium sulfur battery comprising the above separator.
The diaphragm provided by the invention comprises the sulfonated siloxane-based graphene aerogel, has the advantages of high strength and elastic modulus, good interface compatibility with electrolyte, high electronic insulation, good flexibility, easiness in processing, good thermal stability and the like, and can effectively prevent shuttle of polysulfide and improve the performance of the battery.
Drawings
The above and other features and advantages of the present invention will become more apparent by describing in detail exemplary embodiments thereof with reference to the attached drawings.
Fig. 1 is a schematic view of the operation principle and microstructure of a separator according to an embodiment of the present invention.
Fig. 2 is a charge and discharge curve of example 1 and comparative example 1.
Fig. 3 is a cycle performance curve for example 1 and comparative example 1.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
The membrane comprises sulfonated siloxane-based graphene aerogel, wherein the sulfonated siloxane-based graphene aerogel comprises graphene oxide, siloxane groups bridging the graphene oxide and sulfonic acid groups. Wherein the siloxane group is
R is C2-5And a sulfonic acid group is attached.
The aerogel is a solid material with the interior cross-linked by a three-dimensional framework structure, and has the characteristics of high porosity, low density, high specific surface area, low thermal conductivity and the like. Graphene aerogel is with advantages such as graphite alkene elastic modulus is high and thermal stability is good, but graphene aerogel and electrolyte compatibility are relatively poor to higher electric conductivity is not suitable for the diaphragm as the battery. Fig. 1 shows the working principle of the sulfonated siloxane-based graphene aerogel and the microstructure of the sulfonated siloxane-based graphene aerogel, where the sulfonated siloxane-based graphene aerogel of the present invention uses graphene oxide as a substrate, and siloxane groups as bridges to bridge functional groups between the substrates and connect sulfonic acid groups. The graphene oxide provides rigidity, and the siloxane provides flexibility, so that the product has good flexibility and meets the processing requirement. The non-conductive siloxane is connected between the surface of the graphene oxide of the sulfonated siloxane-based graphene aerogel and the sheet layers, so that the electronic insulation property of the sulfonated siloxane-based graphene aerogel can be improved, and the sulfonated siloxane-based graphene aerogel can be used as a diaphragm of a battery. Due to the limitation of synthesis technology, R in the siloxane group of the aerogel is an alkylene group (including a linear or branched alkylene group) with 2-5 carbons, such as ethylene, propylene, butylene, pentylene, and the like. When R is alkylene with 2-5 carbons, the surface of siloxane is grafted with sulfonic group, which can ensure the high-efficiency transmission of lithium ion and is suitable for lithium ion battery. Meanwhile, the pores of the aerogel are rich, and the electrolyte is difficult to wet, so that the wetting and spreading of the electrolyte on the aerogel can be improved due to the siloxane group, the siloxane group can ensure the swing of the sulfonic group, and the smooth transmission of lithium ions can be ensured. Meanwhile, the sulfonic group is grafted on the surface of the siloxane, so that the flexibility of the siloxane can be effectively utilized, the sulfonic group can fully move in the pore structure of the aerogel, and polysulfide can be effectively intercepted. Therefore, the diaphragm provided by the invention contains the sulfonated siloxane-based graphene aerogel, so that the diaphragm has the advantages of high strength and elastic modulus, good interface compatibility, high electronic insulation, good flexibility, capability of effectively blocking shuttle of polysulfide and the like, and the cycle performance, the charge-discharge efficiency and the service life of a battery can be improved by using the diaphragm provided by the invention.
In a preferred embodiment, the sulfonic acid group is present in an amount of 3 to 6% by weight, preferably 4 to 5% by weight, based on the total weight of the sulfonated siloxane-based graphene aerogel. Too high (above 6%) sulfonic acid group content is realized, which causes difficulty in synthesis process; whereas less than 3% does not effectively inhibit the shuttling of polysulfides.
The sulfonated siloxane-based graphene aerogel can be independently used as a diaphragm. It can also be used as an interlayer of a separator, i.e., a separator composed of an intermediate layer formed of sulfonated siloxane-based graphene aerogel and polymer porous membranes disposed on both sides thereof. The polymeric porous membrane may be any suitable polymeric separator for battery separators such as, but not limited to, polyethylene, polypropylene, composite porous membranes, and the like.
The sulfonated siloxane-based graphene aerogel may be prepared by the following method: preparing a dispersion liquid of graphene oxide; a mercapto group-containing silane coupling agent (HS-R-Si (OR)1)3) Adding the dispersion into the dispersion liquid and stirring to form sulfhydrylation graphene hydrogel; and drying the sulfhydrylation graphene hydrogel, placing the dried sulfhydrylation graphene hydrogel in a solution containing an oxidant, and oxidizing sulfhydryl into a sulfonic acid group to obtain the sulfonated siloxane-based graphene hydrogel.
In a preferred embodiment, the mercapto-containing silane coupling agent mercaptohydrocarbylalkoxysilane, such as, but not limited to, one or more of mercaptopropyltrimethoxysilane, mercaptobutylmethyldimethoxysilane, mercaptoethyltrimethoxysilane.
In a preferred embodiment, the solution containing the oxidizing agent is a solution containing hydrogen peroxide and acetic acid. The volume ratio of the hydrogen oxide to the acetic acid is 1: 3-6. When the sulfydryl is oxidized into the sulfonic group by adopting the solution, the reaction condition is mild, and the method is suitable for industrial production. In the solution, acetic acid is used as an active oxygen carrier, active oxygen can be obtained from hydrogen peroxide to generate peracetic acid, and the peracetic acid and the mercapto compound are subjected to redox reaction at a molar ratio of 3:1 to oxidize the mercapto group into a sulfonic acid group. The reaction process generally ensures the excess of acetic acid, and the volume ratio of hydrogen oxide to acetic acid is generally selected to be 1: 3-6 in consideration of practicability. Of course, the oxidizing agent may also be other suitable oxidizing agents, such as nitric acid and the like.
Finally, the method also comprises a step of drying the sulfonated siloxane-based graphene hydrogel. Any suitable drying method may be employed, such as, but not limited to, freeze drying or supercritical drying.
The lithium-sulfur battery adopting the diaphragm has good cycle performance, charge-discharge efficiency and service life.
The present application is further described below by specific examples. However, these examples are only illustrative and do not set any limit to the scope of the present invention.
In the following examples and comparative examples, reagents, materials and instruments used therefor were commercially available unless otherwise specified.
Membrane preparation
Example 1
(1) Preparation of mercapto siloxane based graphene hydrogel
Weighing 150mg of graphene oxide, and dispersing in 50mL of ethanol water solution (v)Ethanol:vWater (W)And (9: 1), uniformly dispersing by ultrasonic to obtain a graphene oxide dispersion liquid with the concentration of 3 mg/mL. And adding 10mL of mercaptopropyltrimethoxysilane into the system, and stirring for 20min at 120 ℃ to obtain the sulfhydrylated graphene hydrogel.
(2) Preparation of sulfonated siloxane-based graphene hydrogel
The gel was cut into a film having a thickness of 1.0cm and dried in a vacuum oven at 100 ℃ for 24 hours. Soaking the film in 30% H after drying2O2In HOAc solution (H)2O2The volume ratio of the sulfonated siloxane-based graphene hydrogel to HOAc can be 1: 3), reacting for 8h at 50 ℃, and obtaining the sulfonated siloxane-based graphene hydrogel after imbibition swelling and sulfydryl oxidation.
(3) Preparation of sulfonated siloxane-based graphene aerogel
And (3) freeze-drying the synthesized sulfonated siloxane-based graphene hydrogel for 48 hours at the temperature of-50 ℃ to obtain a sulfonated siloxane-based graphite aerogel film with the thickness of 1.0 cm.
Example 2
(1) Preparation of mercapto siloxane based graphene hydrogel
50mg of graphene oxide is weighed and dispersed in 50mL of ethanol water solution (v)Ethanol:vWater (W)1: 9), uniformly dispersing by ultrasonic to obtain graphite oxide with the concentration of 1mg/mLAn alkene dispersion. 5mL of mercaptobutylmethyldimethoxysilane is added into the system, and the mixture is stirred for 60min at 80 ℃ to obtain the sulfhydrylated graphene hydrogel.
(2) Preparation of sulfonated siloxane-based graphene hydrogel
The gel was cut into a film having a thickness of 1.0cm and dried in a vacuum oven at 80 ℃ for 24 hours. Soaking the film in 30% H after drying2O2In HOAc solution (H)2O2The volume ratio of the sulfonated siloxane-based graphene hydrogel to HOAc can be 1: 5), reacting for 4h at 80 ℃, and obtaining the sulfonated siloxane-based graphene hydrogel after imbibition swelling and sulfydryl oxidation.
(3) Preparation of sulfonated siloxane-based graphene aerogel
And (3) freeze-drying the synthesized sulfonated siloxane-based graphene hydrogel for 48 hours at the temperature of-70 ℃ to obtain a sulfonated siloxane-based graphite aerogel film with the thickness of 1.0 cm.
Example 3
(1) Preparation of mercapto siloxane based graphene hydrogel
100mg of graphene oxide is weighed and dispersed in 50mL of ethanol water solution (v)Ethanol:vWater (W)And (9: 1), uniformly dispersing by ultrasonic to obtain a graphene oxide dispersion liquid with the concentration of 2 mg/mL. And adding 8mL of mercaptoethyltrimethyl oxysilane into the system, and stirring at 100 ℃ for 40min to obtain the sulfhydrylated graphene hydrogel.
(2) Preparation of sulfonated siloxane-based graphene hydrogel
The gel was cut into a film having a thickness of 1.0cm and dried in a vacuum oven at 90 ℃ for 24 hours. Soaking the film in 30% H after drying2O2In HOAc solution (H)2O2The volume ratio of the sulfonated siloxane-based graphene hydrogel to HOAc can be 1: 6), reacting for 6h at 60 ℃, and obtaining the sulfonated siloxane-based graphene hydrogel after imbibition swelling and sulfydryl oxidation.
(3) Preparation of sulfonated siloxane-based graphene aerogel
And (3) freeze-drying the synthesized sulfonated siloxane-based graphene hydrogel for 48 hours at the temperature of-70 ℃ to obtain a sulfonated siloxane-based graphite aerogel film with the thickness of 1.0 cm.
Comparative example 1
(1) Preparation of alkylated graphene hydrogel
Weighing 150mg of graphene oxide, and dispersing in 50mL of ethanol water solution (v)Ethanol:vWater (W)And (9: 1), uniformly dispersing by ultrasonic to obtain a graphene oxide dispersion liquid with the concentration of 3 mg/mL. And adding 10mL of propyl trimethyl oxysilane into the system, and stirring at 120 ℃ for 20min to obtain the alkylated graphene hydrogel.
(3) Alkylated graphene aerogel preparation
Cutting the gel into a film with the thickness of 1.0mm, and freeze-drying the film for 48 hours at the temperature of minus 50 ℃ to obtain the alkylated graphite aerogel film with the thickness of 1.0 mm.
Battery assembly
And assembling the lithium-sulfur battery by adopting a button cell system. The positive electrode of the battery adopts a sulfur-containing electrode plate (the area is 1.13 cm) loaded by aluminum foil2) Wherein the active substance: conductive agent: binder 7: 2: 1. the active substance is a cosulfuric sulfur, sulfur-carbon composite material and the like, and the mass percentage of S is 75 percent; the conductive agent is Super P; the binder is polyvinylidene fluoride (PVDF). The negative electrode used a lithium plate having the same area as the positive electrode, and the electrolyte used 1M LiTFSI/DOL + DME (v: 1). The lithium battery is assembled according to the sequence of a negative electrode shell, a lithium sheet, an aerogel film, a positive electrode, a gasket, an elastic sheet and a positive electrode shell, and the addition of electrolyte liquid is 5 mL. And after the battery is assembled, standing for 12h for testing.
Electrochemical testing
The prepared button cell adopts blue charge-discharge test equipment to perform constant-current 0.1C/0.1C charge-discharge test at normal temperature, and the test results are shown in table 1 and figures 2-3.
TABLE 1 Performance of aerogel thin films prepared in examples 1-3 and comparative example 1 after cell assembly
It can be seen from table 1 and fig. 2-3 that the first discharge capacity, coulombic efficiency, and capacity retention after 20 cycles of the battery were significantly improved using the separator of the present invention compared to the alkylated aerogel separator.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (10)
1. A membrane comprising a sulfonated siloxane-based graphene aerogel, the sulfonated siloxane-based graphene aerogel comprising graphene oxide, siloxane groups bridging the graphene oxide, and sulfonic acid groups;
wherein the siloxane group is
R is C2-5And linking the sulfonic acid group.
2. The membrane according to claim 1, wherein the sulfonic acid group content is 3-6% by weight, preferably 4-5% by weight, based on the total weight of the sulfonated siloxane-based graphene aerogel.
3. The membrane according to claim 1, wherein the membrane is composed of an intermediate layer formed of the sulfonated siloxane-based graphene aerogel and polymer porous membranes disposed on both sides thereof.
4. A method for preparing the separator according to any one of claims 1 to 3, comprising:
preparing a dispersion liquid of graphene oxide;
adding a silane coupling agent containing sulfydryl into the dispersion liquid and stirring to form sulfhydrylated graphene hydrogel; and
and drying the sulfhydrylation graphene hydrogel, then placing the dried sulfhydrylation graphene hydrogel in a solution containing an oxidant, and oxidizing sulfhydryl into a sulfonic acid group to obtain the sulfonated siloxane-based graphene hydrogel.
5. The production method according to claim 4, characterized in that the mercapto group-containing silane coupling agent of the compound containing mercapto group is mercaptohydrocarbylalkoxysilane; preferably one or more of mercaptopropyltrimethoxysilane, mercaptobutylmethyldimethoxysilane and mercaptoethyltrimethoxysilane.
6. The production method according to claim 4, characterized in that the solution containing an oxidizing agent is a solution containing hydrogen peroxide and acetic acid.
7. The production method according to claim 6, wherein the volume ratio of the hydrogen peroxide to the acetic acid in the solution containing the oxidizing agent is 1: 3 to 6.
8. The method of claim 4, further comprising a step of drying the sulfonated siloxane-based graphene hydrogel.
9. The method for preparing the sulfonated siloxane-based graphene hydrogel according to claim 8, wherein the sulfonated siloxane-based graphene hydrogel drying step adopts freeze drying or supercritical drying.
10. A lithium-sulfur battery comprising the separator according to any one of claims 1 to 3.
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Cited By (4)
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| CN112038552A (en) * | 2020-09-29 | 2020-12-04 | 荣晓晓 | Bacterial cellulose composite lithium-sulfur battery diaphragm |
| CN113451553A (en) * | 2021-06-09 | 2021-09-28 | 深圳市量能科技有限公司 | Secondary battery, winding core, positive plate and corresponding manufacturing method |
| CN115117553A (en) * | 2022-07-28 | 2022-09-27 | 欣旺达电动汽车电池有限公司 | Functionalized diaphragm and preparation method and application thereof |
| CN115224435A (en) * | 2022-04-28 | 2022-10-21 | 中材锂膜(宁乡)有限公司 | Graphene hydrogel/polyolefin-based lithium ion battery composite diaphragm |
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Address after: 166 Kejiao Road, Jintan District, Changzhou City, Jiangsu Province Applicant after: Kaibo Energy Technology Co.,Ltd. Address before: 166 Kejiao Road, Jintan District, Changzhou City, Jiangsu Province Applicant before: CHINA AVIATION LITHIUM BATTERY RESEARCH INSTITUTE Co.,Ltd. Address after: 166 Kejiao Road, Jintan District, Changzhou City, Jiangsu Province Applicant after: AVIC Innovation Technology Research Institute (Jiangsu) Co.,Ltd. Address before: 166 Kejiao Road, Jintan District, Changzhou City, Jiangsu Province Applicant before: Kaibo Energy Technology Co.,Ltd. |
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| GR01 | Patent grant | ||
| GR01 | Patent grant |