TW595033B - Composition of polymer electrolyte for lithium ion battery and method of making compounds therein - Google Patents

Abstract

A composition of polymer electrolyte for lithium ion battery having excellent electric conductivity and comprising polymer, lithium salt, organic solvent, and a special organic compound having a structure of hydroxyl benzoate or benzene sulfonate with long chain alkyl groups, the latter is a new compound. The special organic compound possesses a property of self-combination into a tubular shape. Such a new special organic compound and the method of making thereof are also provided.

Description

譲 、 Invention (The description of the invention should state: the technical field to which the invention belongs, the prior art, the content, the embodiments, and the drawings.) The technical field to which the invention belongs is a lithium ion battery polymer electrolyte composition and System of law. Applied to rechargeable batteries, can improve the conductivity. Prior art Rechargeable batteries commonly used today, such as lithium ion batteries, have electrolytes composed of high molecular polymers, lithium salt organic solvents, and other additives. Among them, the common polymers are polyethers (E0), polyacrylics, polyfluorenes, and polyalkanes. Lithium salts include UC104, LiCF3S03, LiPF6, LiBF4, or LiN (CF3S02) 2. For solvents, there are ethylene glycol carbonate (EC), propylene glycol carbonate (PC), and other high-boiling organic solvents. Related additives are mostly inorganic compounds, and organic compounds are mostly stabilizers. In terms of conductivity test, the room temperature conductivity of traditional polyether (EO) based polymer electrolytes is only 1.6 × 1 (T5 s / cm (the ratio of polyether (E0) to lithium salt is 8): 1). Therefore, it is necessary to add a large amount of lithium salt and organic solvent in order to barely reach 10.3 s / cm. At this time, the ratio of polyether (E0) to lithium salt has reached as high as 1: 60. Add a large amount of Lithium salt will greatly increase the cost and price of the product, and the addition of a large amount of organic solvents will not only increase the chance of battery leakage, but also increase the volume of the battery, limiting the goals of lightness, thinness and shortness. No. 99807772 and U.S. Patent No. 5,326,657 disclose an electrolyte composition including a polymer, a salt, and an organic solvent. The polymer is a hyperbranched polyethers and has an electrical conductivity of 1.0. · 4 s / cm. So there is still a need for improvement. In addition, there has been described in the literature an organic compound that can self-assemble into a tubular shape. For example: by V · Percec / CTiem · Soc · Perkin Trans · 1, 1993, 0 Continued (Please note and use the continuation sheet when the invention description page is insufficient.) Invention description page 2799, 乂 Perkin Trans. 2, 1994, page 31, r, J. Am. CAem. Soc., 1996, 118, p. 9855, and C7 ^ m · «/ · 1999 <: slightly, 3, p. 1070 series discloses an organic compound that can self-assemble into a tubular shape, which is an amphiphilic compound that is lipophilic and hydrophilic. The structure of the compound contains Gallate (hydroxy-benzoic) is a core and a long-chain alkyl group. Hexagonal stacked phase compounds with a liquid crystal arrangement can be obtained. Furthermore, D.L. Gin Author: 4 books CW U997, 119, p. 492 and 乂 Ru Yiyin., 1948, 12, p. 3522, 'Describe the compound of the neoclassic compound with the pre-mixed compound under appropriate conditions' Under appropriate conditions, it can self-assemble to form tube-shaped hexagonal stacked phases, and after making into a thin film, use the crosslinkable group contained in it to perform a polymerized crosslinking reaction. Composite materials. The raw materials used are similar to those of Shangninghua's, but its long-chain frequency base At the end is C-Crylyl IS, which can be used for polymerization or cross-linking reaction. The compounds mentioned above and above all have gallate (via benzoate) as the core. But until now & LX is also delimited It is understood that there have been no reports on the application of such compounds to electrolytes. In addition, the compounds reported in the literature are all compounds with a gallic acid group as the core (for example, in formula ，, the parent is seven paid, As for the compound of formula (i), xiS03m has not been reported yet. SUMMARY OF THE INVENTION The above-mentioned disadvantages of the prior art of polymer electrolytes for ion batteries are to improve the conductivity of lithium ion electrolyte compositions by improving the conductivity of lithium ion electrolytes. Another object is to provide a compound for a polymer electrolyte of a lithium-ion battery. The compound has the characteristics of a self-assembled Gu-nami tubular channel, and 595033 promotes the conductivity of the electrolyte. Yet another object of the present invention is to provide a method for producing a polymer electrolyte for a lithium ion battery polymer of the present invention.

In order to achieve the above-mentioned purpose of improving conductivity, a special compound or a crosslinked polymer thereof is added as a component of a polymer electrolyte composition of a lithium ion battery. Such compounds are reported in the literature and have the characteristics of self-combination to form hollow cylindrical tubular nanotubes. When used in the present invention, unexpectedly, the lithium ion can be transferred more smoothly and the conductivity of the electrolyte can be improved. The chemical structure of this compound contains a hydroxybenzoate core and a long-chain alkyl group, and the long-chain alkyl terminal is connected with a group capable of performing a crosslinking reaction to polymerize. The present invention also provides another novel compound containing a benzenesulfonate as the core and a long-chain alkyl group having a functional group that can be cross-linked to polymerize at the end. When the electrolyte composition of the present invention contains these compounds When the cross-linked polymer is a component, it also has the effect of improving the conductivity. Therefore, the lithium ion battery polymer electrolyte composition of the present invention comprises: (1) a compound of formula (I) or a polymer obtained by a crosslinking reaction of 0.1% to 10% by weight:

Where X is -C02M or -S03M, and M is an alkali metal; R2 is Η or -OR4Y; R1 and R3 are the same or different and are independently -0R4Y; each R4 is the same or different and is-(CH2) n- , Η is an integer from 4 to 20; each fluorene is the same or different and is independently an acrylic-based group, a styrene-based group, or an ethylene oxide-based group; (2) a weight percentage of 5.0% to 40.0 % Of polymers selected from polyethers, polyacrylics, 8-polymers, and polymer groups, and their composition is different from ⑴; (3) The percentage of weight is 3.0% to 100%. % By weight of salt; and (4) organic solvents having a weight percentage of 300% to 800%. The novel invention of the present invention is applicable to a polymer electrolyte compound for an ion battery, which has a chemical structure of the following formula (H):

s〇3M Formula (II) where R2 is Η or -〇r4y; R and R are the same or different and are independently -0R4Y; each R4 is the same or different and is independently _ (CH2) n_, n is 4 to 20 An integer; each Y system, the same or different, is independently an acrylic-based group, a styrene-based group, or an ethylene oxide-based group; and M is a metal test. The novel method for preparing a polymer electrolyte compound suitable for a clock ion battery includes the following steps: Alkali metal salt of 3'4,5-monohydroxybenzenesulfonic acid or 3,5-dihydroxybenzenesulfonic acid And L- (CH2) nZ with 〇 · 〇7 $? Σ # Gan, ^, the molar ratio of the main 2.5 is in an organic solvent, under the condition of weak alkaline (pH = A 〇C), the substitution reaction To form a compound of formula (II), where L rabbit # $, _atomic 'Z is an acrylic group, a styrene group, or a% oxygen = county group, and η is 4 to 2. The conductivity of the polymer electrolyte composition of the bell ion battery of the present invention can easily violate 3 X 10 s / cm, without β ♦ using a large lithium salt or organic solvent, which solves the problems of the prior art. Embodiments The present invention is described in detail below. The lithium ion battery polymer electrolyte composition of the present invention includes the following components (i) to (4), which are described as follows: ⑴ The weight percentage is 0.1% to 10.0%, preferably h: ::. 5% to 3.5% of the formula ™ ^

In formula ⑴ ml, x is -C02MU03M, and M is a metal test (for example, bell, sodium, unloading), preferably bell and sodium. In the formula, r2 is H t0R4Y; R1 and R are independently -0R4Y; each R4 #phase ', σ or different in the bean is 4 to 2 ^^ "different and independent even") is 4 to 20, preferably 8 To 18, and more preferably, ^ ^ an integer of the king 14. Each line is the same or different and is independently an acrylic group, acetophenone group, "^ buccal gang group, or a tick ethane group The group 'is preferably an acrylic group. So the formula ⑴ and ^ can be the same and the plate r2 is different, or R1! ^, And are the same or different, preferably r1, r2, ^ r3 are all the same. In the preparation of polymer electrolytes, for example, irradiation of UV or other methods can be used to make the β-product of the gas () step by step paternity reaction to form a polymer. If the degree of crosslinking is too low (e.g., less than 10 mole%), its ionic conductivity is unstable. When X in formula (I) is -CO2M, it is a known compound, but it has not been used in a high molecular electrolyte, it is commercially available, and it can also be obtained synthetically. XU03M is a novel compound of the present invention. In the present invention, the component (1) may be a compound represented by the formula (I) alone, a mixture of different compounds represented by the formula (I), or a chemical compound represented by the formula (I) alone obtained through a crosslinking reaction. A polymer, a polymer obtained by a cross-linking reaction of a mixture of different compounds represented by formula (I), and combinations thereof. (2) The reset percentage is 5.0% to 40.0%, preferably 100% to 30.0%, and most preferably 15.0% to 25.0% selected from polyethers, polyacrylics, polyalkanes, And its 595033 group of polymers, the composition of which is different from (1); for example, polyethylene glycols, polypropylene glycols, polybutylene glycols, polyacrylonitrile, polyacrylic acid, etc. . (3) The weight percentage is 3.0 ° / ◦ to 10.0%, preferably 4.0% to 8.0%, and most preferably 5.0% to 7.0% lithium salt. The salt is selected from the group consisting of LiC104, LiCF3S03 , LiPF6, LiBF4, LiN (CF3S02) 2, and combinations thereof. (4) Organic solvents with a weight percentage of 30.0% to 80.0%. Organic solvents that can be used are, for example, ethylene glycol carbonate, propylene glycol carbonate, butanediol carbonate, acetonitrile, propionitrile, or a combination thereof.

The above-mentioned polymer electrolyte composition of the lithium ion battery of the present invention can be prepared through the following steps: water and a photo-initiator-containing p-xylene (p-xylene) are added to the monomer of formula (I). The solution of) was centrifuged in a centrifuge, taken out and allowed to stand at room temperature for 24 hours, and then taken out and coated on a glass slide, and then irradiated with UV light for 1 hour, and then dried the solvent and ground it into a powder. Add the above ground powder to the EC / PC electrolyte containing 1 M LiC104 and polymer (such as polyethylene glycol), and make them fully mixed, then the electrolyte composition of the present invention has good conductivity. In formula (I), when X is a sulfonate, formula (I) is a novel compound of the present invention applied to a lithium ion battery polymer electrolyte, that is, it has a chemical structure of the following formula (II):

Where R2 is Η or -0R4Y; 'R1 and R3 may be the same or different and are independently -0R4Y; each R4 is the same or different and is independently-(CH2) n-, η is 4 to 20, preferably 8 to 18, and preferably an integer of 10 to 14; each of the fluorene is the same or different and is independently an acrylic group, a styrene group, or an ethylene oxide group, preferably an acrylic group Groups, which can be used to crosslink compounds of formula (II) 11 595033 to form polymers; and M is a metal detection (eg, warp, sodium, potassium), preferably warp, sodium.

The present invention also relates to a method for manufacturing a compound having the above formula (II). The method comprises the steps of: combining an alkali metal salt of 3,4,5-trihydroxybenzenesulfonic acid or 3,5-dihydroxybenzenesulfonic acid with L- (CH2) nZ is substituted in an organic solvent at a molar ratio of 0.07 to 2.5. The 3,4,5-trihydroxybenzenesulfonic acid or the alkali metal salt of 3,5-dihydroxybenzenesulfonic acid is used in the solvent. The concentration in the solvent is about 0.05 g to 0.5 g per milliliter of solvent, depending on the reactants. Generally, the reaction is performed under the conditions of weak alkaline (for example, pH = 7.5 to 9.0) and 20QC to 80QC to form the formula (II). A compound in which L is a halogen atom, preferably bromine or iodine, Z is an acrylic group, a styrene group, or an ethylene oxide group, preferably an acrylic group, and η is 4 to 20, preferably 8 to 18, and most preferably an integer of 10 to 14. In order to make the above and other objects, features, and advantages of the present invention more comprehensible, preferred embodiments are exemplified below and described in detail as follows: Examples Example 1 Synthesis of Compounds of Formula (II)

ΟΗ 1 ΟΗ

ΟΗ S03Na 2

〇 〇

Add H2S03 (containing 6% S02) aqueous solution to a reaction bottle containing Na2CO3 (10g) until pH = 1 ~ 2, then add compound 1 (5g) and stir under reflux for three days. The solvent is distilled off and the rest The viscous liquid was extracted with ethanol. After filtration, the filtrate was concentrated and washed with ethyl acetate to obtain white solid product 2. 12 595033 Spectral data: IR: 3454, 1634, 1599, 1523, 1497, 1221, 1055 cm · 1 NMR (200 MHz, D2〇) δ: 6.83 (2H) 5 6.52 (1H) 13C NMR (200 MHz, D20) 8: 157.7, 144.5, 106.1, 104.7 If (1.38 g, 10 mmol) of carbonic acid was added to a mixed solution of compound 2 (0.45 g, 2 mmol) and monomethylene maple (DMSO) (6 mL). After stirring at room temperature for 5 hours, 11-Bromoundecyl acrylate (1 28 «MG, 4.2 mmol) was added, and stirring was continued at 80 ° C for 24 hours. After warming, the reaction solution was added to 50 ml of water and extracted with ethyl acetate (50 mix 3). The organic layer was dried, filtered, and concentrated to obtain the sodium benzenesulfonate product of compound 3, which is the formula (II) of the present invention. The novel compound '3,5-bis- (11-propenyloxy undecyloxy) sodium benzosulfonate ({sodium 3,5-bis- (ll'-acryloyloxyundecyloxy) benzenesulfonate), {is a monomer, produced The rate is 70%. Spectral data IR: 3450, 2919, 2852, 1727, 1505, 1423, 1474, 1198, 1031 cm1 lU NMR (200 MHz5 d-DMSO) δ: 6.76 (2H), 6.41-6.15 (5H), 5.99 (2H ), 4 · 12 (4Η), 3.95 (4Η), 1.81-1.25 (36H)

Example 2 Preparation of a polymer electrolyte composition for a lithium ion battery of the present invention (the electrolyte composition uses a compound of formula (II)) At room temperature, 400 mg of the product obtained in Example 1 (ie, formula (II) Compound, 3,5-bis- (11-propenyloxy-undecyloxy) sodium benzothionate, where X = S03Na) as a monomer, put in a bottle, add 50 mg of water and 50 mg of a solution containing 20% by weight of a 2-hydroxy-2-methylpropiophenone photoinitiator in 20% by weight of p-difluorenylbenzene. Seal the outer periphery of the bottle with tin foil and stir well. Put it in a centrifuge and centrifuge (2800 rpm). Put it forward, put it in reverse, and put it upside down. Centrifuge each for 15 minutes. Take it out and let it stand at room temperature for 24 hours. Then, take it out and coat it on a glass slide. Dry solvent and grind to powder. 13 595033 Add 20 mg of the above ground powder to 800 mg of EC / PC (EC / PC = 8/2 v / v) electrolyte containing 200 mg of LiCl〇 and 200 mg of polyethylene glycol (Yako 4 105) After the mixture is sufficiently mixed to form an electrolyte composition, the conductivity is measured ^ ® Example 3 The degraded composition of the polymer electrolyte composition of the lithium ion battery of the present invention uses a compound of formula (I) at room temperature, Take 800 mg of a compound of formula (I) (where X = tri- (11-propenyloxy-undecyloxy) benzoate n ^ (S〇di 2M) 3,4 氺 3,4,5- tris (l 1, -acryloyl〇xyundecyloxy) benzoate) as monomer in a bottle, put 100 ml of water and 100 mg of 2-hydroxy-2-methylphenylpropane-containing light * add wt% The solution of methylbenzene is sealed with tin foil on the periphery of the bottle. Stir and mix well. Centrifuge (2800 rpm) in the centrifuge. After being left at room temperature for 24 hours, it was taken out and coated on a glass slide, and was irradiated with UV light for 1 hour, and then the solvent was drained and ground into a powder. Add 30 mg of the above milled powder to 800 mg of EC / PC (EC / PC = 8/2 v / v) electrolyte containing 1 M LiC104 and 200 mg of polyethylene glycol (molecular weight 105). After being mixed thoroughly, an electrolyte composition was formed, and a conductivity test was performed. Testing of samples

The conductivity of the compositions obtained in Examples 2 and 3 was measured with a general conductivity tester. The results are shown in Table 1.

14 595033 Table 1 Results of various electrolyte tests Electrolyte composition ratio (weight ratio) Ionic conductivity (s / cm) Prior art polyethylene glycol · 1 Μ LiC104 8: 1 1.6χ ι〇-5 Prior art polyethylene Diol · 1M LiC104 1: 4 3.7 x ιο'4 Composition of Example 2 Polyethylene glycol: 1M LiC104: Compound 3 obtained in Example 1 after crosslinking reaction 1: 4: 0.10 4.4 × 10′3 Composition of Example 3 Polyethylene glycol: 1M LiC104: 3,4,5-tri- (11-propenyloxy-undecyloxy) sodium benzoate 1: 4: 0.15 after cross-linking reaction 4.7χ 1〇 * 3 Although the present invention has been disclosed in the preferred embodiment as above, it is not intended to limit the present | Anyone who is familiar with this art after reading the invention will not depart from the spirit of the present invention Within the range, you can make a few changes and retouching. Therefore, the scope of protection of the present invention shall be determined by the scope of the attached patent application. 15 595033 Pickup and diagram

Claims (1)

595033 First, the scope of application for patent 1. A polymer electrolyte composition for lithium ion batteries, including: (1) a compound such as formula ⑴ in a weight ratio of 0.1 to 10%, the polymerization of the compound through a crosslinking reaction Objects, or a combination thereof: Λ formula (I) Where X is -C02M or -S03M, μ is an alkali metal; R2 is Η or -0R4Y; R1 and R3 are the same or different and are independently -0R4Y; each R4 is the same or different and is independent &_; (CH2) n_ , Η is an integer from 4 to 20; each fluorene is the same or different and is independently an acrylic-based group, a styrene-based group, or an ethylene oxide-based group; (2) a weight ratio of 5 to 40% of polymers selected from the group consisting of polyethers, polyacrylics, polyalkanes, and combinations thereof, which are different from component (1); (3) lithium with a weight ratio of 3 to 10% Salt; and (4) Organic solvents with a weight ratio of 30 to 80%. 2. The polymer electrolyte composition for a silk sub-battery according to item 丨 in the scope of the patent application, wherein r4 is-(CH2) n_ and η is an integer from 8 to 18. 3. The polymer electric composition of an ion battery as described in the application #patent | [circle], wherein Ri is the same as R3. 4. The polymer electrical composition of the rotor battery according to item 丨 in the scope of the patent application, wherein R !, R2, and R3 are the same. 1. The polymer electrolyte of sub-cells as described in item i of the patent, and 'wherein the lithium salt is a group selected from the following: Lici〇4, LicF3S〇3, □ Continued' Page (please note and use the continuation page if the patent application page is insufficient) 17 595033 «Please refer to the patent page K. Continued pages UPF6, LiBF4, LiN (CF3S02) 2, and combinations thereof. 2. The polymer electrolyte of the shop battery as described in item i of the patent application, and the product, wherein the organic solvent is ~, 6-, acetonitrile, propionitrile, or a combination thereof. 7. A compound that is used in a battery cell and has the chemical structure of the following formula (II): so3m Formula (II) wherein R2 is Η or -〇r4y; R and R3 are the same or different and are independently -0R4Y; each R is the same or different and are independently, n is an integer of 4 to 20; each Y is the same Or different and independently acrylic-based groups, styrene-based groups, or ethylene oxide-based groups; and M is an alkali metal. 8. The compound as described in item 7 of the scope of patent application, wherein R4 has 8 to 18 carbon atoms. 〃 9. The compound as described in item 7 of the scope of patent application, wherein R1 is the same as R3. 10. The compound as described in item 7 of the scope of patent application, wherein R1, R2, and R3 are the same. 11. The compound as described in item 9 of the scope of patent application, wherein R1 and R3 are CH2CHC (〇) 〇_ (CH2) lr〇-. 12. The compound as described in item 11 of the scope of patent application, wherein R2 is fluorene. 13. · A method for manufacturing a compound of formula (II), which is suitable for a polymer electrolyte of a lithium ion 18 battery 12. S〇3M Formula (11), in which R is Η or -〇R4y · R and R3 are the same or different times and are independently -or4y;, and the same or different are independently · βΗ2) η ·, ^ Is an integer of 4 to 20, and Ul 7 m 7 is the same or different and is independently an acrylic group, a styrenic group or a% ethane group; and M is an alkali metal; the steps include: The alkali metal salt of 3'4,5-dihydroxybenzylsulfonic acid or 3,5-dihydroxybenzenesulfonic acid is compared with (CHA-z in a molar ratio of 0.07 to 2.5 in an organic solvent in alkaline (? 11 =: 7 5 to 〇) and 20 C to 80 ° C, the substitution reaction is carried out to form a compound of the formula: where L is a halogen atom, Z is an acrylic group, benzene An ethylene-based group, or an ethylene oxide-based group, and η is an integer of 4 to 20. 14. The method for producing a compound of formula (II) according to claim 13 in the scope of the application, wherein η is an integer of 8 to 18. 15. A method for producing a compound of formula (11) according to item 13 of the scope of the patent application, wherein L is bromine or iodine. 16. The method for producing a compound of formula (11) as described in item π of the patent application range, wherein Z is an acrylic group. 19