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WO2025063892A1 - Composition et matériau composite - Google Patents

Composition et matériau composite Download PDF

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Publication number
WO2025063892A1
WO2025063892A1 PCT/SG2024/050599 SG2024050599W WO2025063892A1 WO 2025063892 A1 WO2025063892 A1 WO 2025063892A1 SG 2024050599 W SG2024050599 W SG 2024050599W WO 2025063892 A1 WO2025063892 A1 WO 2025063892A1
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WO
WIPO (PCT)
Prior art keywords
composition
composite material
compound
organo
bis
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/SG2024/050599
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English (en)
Inventor
Derrick FAM
Yuanhuan ZHENG
Ming Yan TAN
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Agency for Science Technology and Research Singapore
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Agency for Science Technology and Research Singapore
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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Publication of WO2025063892A1 publication Critical patent/WO2025063892A1/fr
Pending legal-status Critical Current
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
    • C08G75/02—Polythioethers
    • C08G75/04—Polythioethers from mercapto compounds or metallic derivatives thereof
    • C08G75/045—Polythioethers from mercapto compounds or metallic derivatives thereof from mercapto compounds and unsaturated compounds
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type

Definitions

  • the present invention further relates to a composite material, a method of forming the same and an electrochemical device comprising the same.
  • SPE systems consist of a highly flexible polymeric network that contains lithium salt dispersed within the matrix. These polymeric networks categorically contain large amount of ethoxy functional groups and these ethoxylations serve as “hopping” sites for Li-ion migration within the SPE systems.
  • high molecular weight PEGylated materials are dispersed within the matrix to increase the quantities of “hopping” sites.
  • this boost in ion conductivity comes at a price, as the storage modulus of these system degrades as the increased in ethoxy groups increase chain flexibility in the polymeric matrix, resulting in a tacky film. At elevated temperatures, the high molecular PEGylated materials would melt and plasticize the polymeric matrix, causing a reduction in storage modulus.
  • the present method is easy to operate as it may be done in a one-pot manner.
  • the present composite material may have an ion conductivity of more than 10 5 S cm 1 and an electrochemical stability window of more than 4 V. This is because of the use of the organo-ionic compound which is partially bound to a polymeric matrix and partially moving freely.
  • the present composite material may be considered as “non-leaky”. This is due to the presence of a strong interaction between cationic groups and anionic groups from the organo-ionic compound which prevents leaching from the composite material, which is commonly faced in conventional composite materials.
  • the present composite material may be regarded as a free-standing or solid-state material. Therefore, it does not require an additional structural casing as support.
  • the present composite material may have a low fire hazard as it may not comprise flammable liquids.
  • an electrochemical device comprising the composite material as described herein.
  • organo-ionic compound refers to an organic compound comprising both cationic groups and anionic groups. Therefore, an organo-ionic compound may also be regarded as an organic salt of the cationic groups and anionic groups.
  • poly-thiol compound refers to an organic compound comprising a plurality of thiol groups.
  • thiol group refers to a terminal -SH group. Therefore, the term “thiol group” is interchangeable with -SH and sulfhydryl group.
  • Non-limiting examples of the groups above include acrylic acid, acrylate, acrylamide, allyl, vinyl, ethylene, and the like.
  • range format may be disclosed in a range format. It should be understood that the description in range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the disclosed ranges. Accordingly, the description of a range should be considered to have specifically disclosed all the possible sub-ranges as well as individual numerical values within that range. For example, description of a range such as from 1 to 6 should be considered to have specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6 etc., as well as individual numbers within that range, for example, 1, 2, 3, 4, 5, and 6. This applies regardless of the breadth of the range. Certain embodiments may also be described broadly and generically herein.
  • the composition may further comprise a lithium salt.
  • the lithium salt may advantageously dissolve in the organo-ionic compound to form a homogenous mixture. Therefore, the composition may be formed into a lithium battery, where the lithium salt serves as conducting species.
  • the lithium salt may exemplarily be, but not limited to, lithium triflate (LiTRF), lithium bis(trifluoromcthancsulfonyl)imidc (LiTFSI), and a combination thereof.
  • LiTRF lithium triflate
  • LiTFSI lithium bis(trifluoromcthancsulfonyl)imidc
  • the composition may further comprise a polymerisation initiator.
  • the photo initiator may be selected from the group consisting of methyl benzoylformate, 2,2-dimethoxy-2-phenylacetophenone, 2,4,6- tris(dimethylaminomethyl)phenol, 4-thiophenyl phenyl diphenyl sulfonium hexafluoroantimonate (TPSHA), diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (DTPO), 4-(dimethylamino) pyridine, 2-hydroxy-2-methylpropiophenone (HMPP) and combinations thereof.
  • TPSHA 4-thiophenyl phenyl diphenyl sulfonium hexafluoroantimonate
  • DTPO diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide
  • HMPP 2-hydroxy-2-methylpropiophenone
  • the composition may not comprise any acrylate or derivatives thereof.
  • a Type T photo initiator e.g., 2,2-dimethoxy-2-phenylacetophenone or 2- hydroxy-2-methylpropiophenone
  • a thermal initiator e.g., azobisisobutyronitrile
  • the polymerisation initiator is abase or a nucleophile (e.g., 4-(dimethylamino) pyridine or DTPO) and one or more acrylates are present (e.g., in the bridging compound)
  • the C-C double bonds will be completely reacted upon curing of the composition. Therefore, when the organo-ionic compound is incorporated into the polymeric matrix via the at least one C-C double bond, each molecule of the organo- ionic compound will be partially bound to the polymeric matrix. This may avoid the formation of a semi-solid electrolyte that is “leaky” due to elution of unbound molecules of the organo-ionic compound. A “leaky” electrolyte will lead to a loss of cation inventory and hence a degradation in material performance (c.g. if employed in a battery, a degradation in capacity).
  • the organo-ionic compound may have a molar percentage in the range of about 12 mol% to about 37 mol%, about 20 mol% to about 37 mol%, about 30 mol% to about 37 mol%, about 12 mol% to about 30 mol% or about 12 mol% to about 20 mol%, based on the total number of moles of compounds in the composition.
  • the poly-thiol compound may have a molar percentage in the range of about 20 mol% to about 35 mol%, about 25 mol% to about 35 mol%, about 30 mol% to about 35 mol%, about 20 mol% to about 30 mol% or about 20 mol% to about 25 mol%, based on the total number of moles of compounds in the composition.
  • the bridging compound may have a molar percentage in the range of about 5 mol% to about 18 mol%, about 10 mol% to about 18 mol%, about 15 mol% to about 18 mol%, about 5 mol% to about 15 mol% or about 5 mol% to about 10 mol%, based on the total number of moles of compounds in the composition.
  • the lithium salt (where present) may have a concentration in the range of about 1 M to about 1.5 M, about 1.2 M to about 1.5 M or about 1 M to about 1.2 M based on the total volume of the organo-ionic compound.
  • the polymerisation initiator (where present) may have a molar percentage in the range of about 0.5 mol% to about 5 mol%, about 3 mol% to about 5 mol% or about 0.5 mol% to about 3 mol%, based on the total number of moles of compounds in the composition.
  • the method comprises the steps of:
  • step (b) curing the composition of step (a) to form the composite material.
  • the method may be undertaken in a one-pot system.
  • composition may further comprise a polymerisation initiator to aid the curing step (b) where the composition is polymerised.
  • the composite material may be in the form of a homogeneous gel film.
  • the composite material may be regarded as or used as a polymer electrolyte.
  • the composite material When a voltage is applied to the composite material, the part of the organo-ionic compound that is freely moving gains mobility and form pseudo-percolation channels that aid migration of lithium ions. Therefore, the composite material may have a higher ionic conductivity than conventional solid polymer electrolytes.
  • the composite material may not comprise flammable liquids.
  • the composite material may have an electrochemical stability window of more than 4 V.
  • the present composite material may have a high ionic conductivity and electrochemical stability window with a relatively low concentration of lithium salt (e.g., about 1 M) due to the use of the organo-ionic compound as described above.
  • a relatively low concentration of lithium salt e.g., about 1 M
  • the electrochemical device comprises the composite material as described herein.
  • the electrochemical device may be a battery.
  • FIG. 1 A first figure.
  • FIG. 1 shows a moiety comprised in an embodiment of the composite material as described herein.
  • FIG. 2 shows an illustration of an embodiment of the composite material as described herein.
  • an organo-ionic compound, a poly-thiol compound, a bridging compound, a polymerisation initiator and a lithium salt were blended mechanically in a one-pot system until the lithium salt was fully dissolved and the mixture was fully homogeneous to form a composition.
  • the concentration of the lithium salt as dissolved in the organo-ionic compound (which was used as a solvent and an electrolyte) was kept at 1 M.
  • the polymerization initiator was added at about 3 weight% based on the total weight of all chemicals used in the one-pot system.
  • composition was subsequently cast into a silicone mold, followed by curing either thermally (at about 70 °C for about 1 hour) or via U V initiation (using a U V radiation source which was more than 30 mM for about 10 minutes).
  • thermally at about 70 °C for about 1 hour
  • U V initiation using a U V radiation source which was more than 30 mM for about 10 minutes.
  • Organo-ionic compound - 1 -allyl- 3-methylimidazolium bis(trifluoromethanesulfonyl)imide (AMF, purchased from Sigma Aldrich, Singapore and Tokyo Chemical Industry Co, Tokyo, Japan)
  • AMF Organo-ionic compound - 1 -allyl- 3-methylimidazolium bis(trifluoromethanesulfonyl)imide
  • AMF 1,3-bis(trifluoromethanesulfonyl)imide
  • ABS 1-butylimidazolium bis(trifluoromethanesulfonyl)imide
  • Poly-thiol compound - dipcntacrythritol hcxakis(3-mcrcaptopropionatc) (DPHS, purchased from Sigma Aldrich, Singapore and Tokyo Chemical Industry Co, Tokyo, Japan)
  • DPHS dipcntacrythritol hcxakis(3-mcrcaptopropionatc)
  • PTS pcntacrythritol tctrakis(3 -mercaptopropionate
  • Bridging compound - trimethylolpropane ethoxylate triacrylate (TMET, purchased from Sigma Aldrich, Singapore and Tokyo Chemical Industry Co, Tokyo, Japan), triiclhylcnc glycol) divinyl ether (TDV, purchased from Sigma Aldrich, Singapore and Tokyo Chemical Industry Co, Tokyo, Japan), trimcthylolpropanc diallyl ether (TMPD, purchased from Sigma Aldrich, Singapore and Tokyo Chemical Industry Co, Tokyo, Japan), diallyl carbonate (DAC, purchased from Sigma Aldrich, Singapore and Tokyo Chemical Industry Co, Tokyo, Japan), polyethylene glycol dimethacrylate (PEGDMA, purchased from Sigma Aldrich, Singapore and Tokyo Chemical Industry Co, Tokyo, Japan).
  • TMET Trimethylolpropane ethoxylate triacrylate
  • TDV triiclhylcnc glycol) divinyl ether
  • TDV triiclhylcnc glycol) divinyl ether
  • TDV triiclhylcnc glycol) divin
  • HMPP 2-hydroxy-2-methylpropiophenone
  • Lithium salt - lithium bis(trifluoromcthancsulfonyl)imidc LiTFSI, purchased from Sigma Aldrich, Singapore and Tokyo Chemical Industry Co, Tokyo, Japan.
  • Table lb Formulation of composite materials with different electrolytes and polythiol compound loaded Table 1c. Ion conductivities (IC) and electrochemical stability window (ECV) of the composite materials formed
  • the bridging compound was fixed as tri(ethylene glycol) divinyl ether (TDV) to allow comparison of the electrolyte and the poly-thiol compound used.
  • TDV tri(ethylene glycol) divinyl ether
  • Sample VEC-2 was prepared using a non-partially bounded electrolyte, vinyl ethylene carbonate (VEC); which could not form pseudo percolation channels within the material under a potential difference. This resulted in a severe degradation in ion conductivity.
  • VEC vinyl ethylene carbonate
  • Sample B2 was prepared with l-allyl-3-butylimidazolium bis(trifluoromethylsulfonyl)imide (ABF) electrolyte, with a longer butyl side group attached to the imidazolium as compared to methyl group in l-allyl-3- methylimidazolium bis(trifluoromethanesulfonyl)imide (AMF).
  • ABSF l-allyl-3-butylimidazolium bis(trifluoromethylsulfonyl)imide
  • Sample A2 had a higher measured Li-ion conductivity. This phenomenon could be explained by sample D2 being constituted by DPHS possessing 6 thiol groups per DPHS molecules as compared to 4 thiol groups per molecule for PTS in sample A2. This implies that density of cross-linking per volume within the film was higher in D2 than A2, which resulted in an increase in polymeric matrix stiffness of the D2 battery electrolyte film as compared to A2. This further resulted in a reduction of Li-ion conductivity. Likewise, the higher density of cross-linking per volume of D2 also caused D2 to be more resilient to oxidative degradation as compared to A2, resulting in a higher ECV to be measured.
  • VEC Vinyl Ethylene Carbonate

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Electrochemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Secondary Cells (AREA)

Abstract

L'invention concerne une composition comprenant un composé organo-ionique comprenant au moins une double liaison C=C, un composé polythiol comprenant une pluralité de groupes thiol et un composé de pontage comprenant une pluralité de doubles liaisons C=C. L'invention concerne en outre un matériau composite, un procédé de formation de celui-ci et un dispositif électrochimique comprenant celui-ci.
PCT/SG2024/050599 2023-09-21 2024-09-19 Composition et matériau composite Pending WO2025063892A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SG10202302665X 2023-09-21
SG10202302665X 2023-09-21

Publications (1)

Publication Number Publication Date
WO2025063892A1 true WO2025063892A1 (fr) 2025-03-27

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140234727A1 (en) * 2011-10-17 2014-08-21 Ube Industries, Ltd. Non-aqueous electrolyte solution and electricity-storage device using same
US20160304662A1 (en) * 2013-12-18 2016-10-20 Dow Global Technologies Llc Process for forming an organic polymer in a reaction of a polyene, an epoxy resin and a mixture of thiol and amine curing agents
CN106432727A (zh) * 2016-09-18 2017-02-22 中国人民解放军国防科学技术大学 一种以咪唑类离子液作为交联剂制备电荷梯度及疏水性梯度阳离子型聚合物抗菌膜的方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20140234727A1 (en) * 2011-10-17 2014-08-21 Ube Industries, Ltd. Non-aqueous electrolyte solution and electricity-storage device using same
US20160304662A1 (en) * 2013-12-18 2016-10-20 Dow Global Technologies Llc Process for forming an organic polymer in a reaction of a polyene, an epoxy resin and a mixture of thiol and amine curing agents
CN106432727A (zh) * 2016-09-18 2017-02-22 中国人民解放军国防科学技术大学 一种以咪唑类离子液作为交联剂制备电荷梯度及疏水性梯度阳离子型聚合物抗菌膜的方法

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