Novel polymer compounds grafted with anion acceptor and secondary battery electrode binders comprising same

Abstract

The present invention relates to novel chitosan polymer compounds and novel electrically conductive polymer compounds substituted with a novel electron-withdrawing group. More specifically, the present invention relates to: novel polymer compounds composed of mixtures of compositions selected from novel chitosan polymer compounds and novel electrically conductive polymer compounds, in which an electron-withdrawing group is introduced into a chitosan polymer or electrically conductive polymer, thereby improving the ionic conductivity and cation transport number of binders to which same are added and increasing the electrochemical stability of an alkali metal battery using these binders; and secondary battery electrode binders comprising these compounds.

Description

Novel polymer compounds grafted with anion acceptors and binders for secondary battery electrodes comprising the same

[0001] The present invention relates to a novel polymer compound grafted with an anion acceptor and a binder for a secondary battery electrode containing the same.

[0002] Anion acceptors enhance anion stability through Lewis acid-salt interactions. These anion acceptors are compounds containing electron-deficient atoms (N, B) that facilitate the movement of lithium cations by coordinating electron-rich anions around them, thereby hindering the binding of anions and lithium cations into ion pairs. The first known compounds as anion acceptors are aza-ethers composed of cyclic or linear amides, in which the nitrogen atom of an amine group substituted by a perfluoroalkylsulfonyl substituent is made electron-deficient, allowing it to interact appropriately with electron-rich anions through Coulomb attraction (J. Electrochem. Soc., 143 (1996) 3825, 146 (2000) 9). However, these aza-ethers exhibit limited solubility in polar solvents adopted as typical non-aqueous electrolytes, and the electrochemical stability window of the electrolyte with added LiCl salt does not meet the 4.0 V required for commercially available cathode materials. In addition, it has been found that aza-ethers are unstable in LiPF6 (J. Electrochem. Solid-State Lett., 5 (2002) A248). That is, LiPF6 is chemically and thermally unstable and is in equilibrium with solid LiF and gaseous PF5 even at room temperature, and the generation of this gaseous product, PF5, further tilts the equilibrium toward the formation of PF5.

[0003]

[0004] In non-aqueous solvents, PF5 tends to initiate a series of reactions, such as ring-opening polymerization or the breaking of ether bonds composed of atoms with non-covalent electron pairs, such as oxygen or nitrogen. As a strong Lewis acid, PF5 attacks electron pairs, and since aza-ethers have a high electron density, they become subject to immediate attack by PF5 (J. Power Sources, 104 (2002) 260). This poses a significant limitation to the commercialization of aza-ether compounds. Due to this limitation, McBreen et al. synthesized an anion acceptor in which boron was selected as the electron-deficient atom and substituted with an electron-attracting functional group using the same means (J. Electrochem. Soc., 145 (1998) 2813, 149 (2002) A1460).

[0005] Lithium-ion batteries used in electric vehicles are required to operate at high temperatures and possess excellent discharge capacity and lifespan characteristics; to improve these performances, research on binders constituting lithium-ion batteries is also actively underway, in addition to anode and cathode materials.

[0006] A mixture of Na-CMC (sodium carboxymethyl cellulose) and water-dispersed SBR (styrene-butadiene rubber) is used as an electrode binder in lithium secondary batteries. Na-CMC is essential because it maintains the dispersibility of the active material and slurry stability, while water-dispersed SBR is essential because it improves the flexibility of the electrode plate and the adhesion of the active material layer to the substrate. However, since these materials lack electrical and ionic conductivity, they act as resistors within the battery, which negatively affects the battery's lifespan, thus requiring improvement.

[0007] Therefore, an improved binder material is required that solves at least some of the aforementioned problems.

[0008] To solve the aforementioned problems, the present invention provides a novel chitosan polymer compound substituted with an electron-withdrawing group and a novel electrically conductive polymer compound.

[0009] In addition, the present invention provides a binder comprising a novel chitosan polymer compound and an electrically conductive polymer compound.

[0010] According to one embodiment of the present invention, the invention relates to novel chitosan polymer compounds represented by the following chemical formulas 1 to 7.

[0011] [Chemical Formula 1]

[0012]

[0013] [Chemical Formula 2]

[0014]

[0015] [Chemical Formula 3]

[0016]

[0017] [Chemical Formula 4]

[0018]

[0019] [Chemical Formula 5]

[0020]

[0021] [Chemical Formula 6]

[0022]

[0023] [Chemical Formula 7]

[0024]

[0025] (In the above chemical formulas 1 to 7,

[0026] The above X1 and X2 is selected from electron-withdrawing functional groups selected from hydrogen, -SO2CF3, -COCF3, -SO2CN, -CF3, and -CN, respectively, and

[0027] Y is selected from hydrogen and -COOH, and

[0028] R1, R2, R3, and R4 are identical or different from one another and each independently a hydrogen atom, a substituted or unsubstituted C1 to C5 alkyl, or -(CH2) p -COOX 1 (p is 1 to 5, and X 1 It is an alkali metal, and

[0029] R5, R6, R7, and R8 are identical or different from each other and are each independently H or COOH, and at least one of R5, R6, R7, and R8 is COOH,

[0030] m, n, and o are integers from 10 to 10,000.

[0031] According to one embodiment of the present invention, the present invention relates to a novel chitosan polymer compound comprising at least one of the compounds represented by Formulas 1 to 7 according to the present invention.

[0032] According to one embodiment of the present invention, the invention relates to a novel electrically conductive polymer compound represented by the following chemical formulas 8 to 9.

[0033] [Chemical Formula 8]

[0034]

[0035] [Chemical Formula 9]

[0036]

[0037] The above X is selected from electron-withdrawing functional groups selected from -SO2CF3, -COCF3, -SO2CN, -CF3, and -CN; and

[0038] Y is selected from hydrogen and -COOH, and

[0039] R1, R 10 , R 11 , R 12is a linear or branched alkyl group having 1 to 20 carbon atoms or an alkenyl group having 2 to 20 carbon atoms, and m and n are integers from 10 to 10,000.

[0040] The present invention provides a novel chitosan polymer compound substituted with an electron-withdrawing group and a novel electrically conductive polymer compound.

[0041] In addition, the present invention provides a binder for a secondary battery electrode comprising a novel chitosan polymer compound and a novel electrically conductive polymer compound according to the present invention.

[0042] Accordingly, the present disclosure provides an electrode binder having improved features, a method for manufacturing the same, and an energy storage device comprising the same that overcomes at least some of the problems described in the present specification.

[0043] The present invention improves the ionic conductivity and cation transport rate of binders and enhances the electrochemical stability of alkali metal batteries using these binders.

[0044] FIG. 1 is an example drawing of a binder that accommodates the expansion of an active material during a lithiation / delithiation process,

[0045] FIG. 2 is a graph showing the 200-cycle capacity retention rate of a Si / NCM811 full cell to which a binder according to the present invention is applied.

[0046] FIG. 3 is a graph showing anode capacity retention with a binder applied according to the present invention,

[0047] Figure 4 is a graph showing the anode charge transfer resistance (Rct) with the binder according to the present invention applied.

[0048]

[0049] Hereinafter, embodiments are described in detail with reference to the attached drawings. However, various modifications may be made to the embodiments, and thus the scope of the patent application is not limited or restricted by these embodiments. It should be understood that all modifications, equivalents, and substitutions to the embodiments are included within the scope of the rights.

[0050] The terms used in the embodiments are for illustrative purposes only and should not be interpreted as intended to be limiting. Singular expressions include plural expressions unless the context clearly indicates otherwise. In this specification, terms such as “include” or “introduce” are intended to indicate the presence of the features, numbers, steps, actions, components, parts, or combinations thereof described in the specification, and should be understood as not precluding the existence or addition of one or more other features, numbers, steps, actions, components, parts, or combinations thereof.

[0051] Terms such as "first" or "second" may be used to describe various components, but the components shall not be limited by the terms. For the sole purpose of distinguishing one component from another, the terms may, for example, name the first component the second component, and similarly, name the second component the first component.

[0052] Unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as generally understood by those skilled in the art to which the embodiments pertain. Terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with their meaning in the context of the relevant technology, and should not be interpreted in an ideal or overly formal sense unless explicitly defined in this application.

[0053] In addition, when describing with reference to the attached drawings, identical components are assigned the same reference numeral regardless of drawing symbols, and redundant descriptions thereof are omitted. In describing the embodiments, if it is determined that a detailed description of related prior art could unnecessarily obscure the essence of the embodiments, such detailed description is omitted.

[0054]

[0055] Hereinafter, the novel chitosan polymer compound containing an anion acceptor and the novel electrically conductive polymer compound of the present invention, the method for manufacturing the same, and the application thereof will be described in detail with reference to the examples and drawings. However, the present invention is not limited to these examples and drawings.

[0056] The present invention provides a novel chitosan-based polymer compound substituted with an electron-withdrawing group and a novel electrically conductive polymer compound.

[0057] In addition, the present invention provides a binder for a secondary battery electrode comprising a novel chitosan polymer compound and a novel electrically conductive polymer compound according to the present invention.

[0058]

[0059] The present invention relates to a chitosan polymer compound containing a novel anion acceptor.

[0060] According to one embodiment of the present invention, the polymer compound may be a novel chitosan polymer compound grafted with a novel anion acceptor, and may be a novel chitosan polymer compound in which an electron withdrawing group is introduced to a nitrogen atom.

[0061] According to one embodiment of the present invention, the present invention relates to a novel chitosan polymer compound comprising at least one of the compounds represented by the following chemical formulas 1 to 7.

[0062] [Chemical Formula 1]

[0063]

[0064] [Chemical Formula 2]

[0065]

[0066] [Chemical Formula 3]

[0067]

[0068] [Chemical Formula 4]

[0069]

[0070] [Chemical Formula 5]

[0071]

[0072] [Chemical Formula 6]

[0073]

[0074] [Chemical Formula 7]

[0075]

[0076] (In the above chemical formulas 1 to 7,

[0077] The above X1 and X2 is selected from electron-withdrawing functional groups selected from hydrogen, -SO2CF3, -COCF3, -SO2CN, -CF3, and -CN, respectively, and

[0078] Y is selected from hydrogen and -COOH, and

[0079] R1, R2, R3, and R4 are identical or different from one another and each independently a hydrogen atom, a substituted or unsubstituted C1 to C5 alkyl, or -(CH2) p -COOX 1 (p is 1 to 5, and X 1 It is an alkali metal, and

[0080] R5, R6, R7, and R8 are identical or different from each other and are each independently H or COOH, and at least one of R5, R6, R7, and R8 is COOH,

[0081] m, n, and o are integers from 10 to 10,000.

[0082]

[0083] As an example of the present invention, the compound represented by Formula 1 may be selected from Formulas 1-1 to 1-4 below.

[0084] [Chemical Formula 1-1]

[0085]

[0086] [Chemical Formula 1-2]

[0087]

[0088] [Chemical Formula 1-3]

[0089]

[0090] [Chemical Formula 1-4]

[0091]

[0092] As an example of the present invention, the compound represented by Formula 2 may be selected from Formulas 2-1 to 2-4 below:

[0093] [Chemical Formula 2-1]

[0094]

[0095] [Chemical Formula 2-2]

[0096]

[0097] [Chemical Formula 2-3]

[0098]

[0099] [Chemical Formula 2-4]

[0100]

[0101] As an example of the present invention, the compound represented by Formula 3 may be selected from Formulas 3-1 to 3-4 below:

[0102] [Chemical Formula 3-1]

[0103]

[0104] [Chemical Formula 3-2]

[0105]

[0106] [Chemical Formula 3-3]

[0107]

[0108] [Chemical Formula 3-4]

[0109]

[0110] As an example of the present invention, the compound represented by Formula 4 may be selected from Formulas 4-1 to 4-4 below:

[0111] [Chemical Formula 4-1]

[0112]

[0113] [Chemical Formula 4-2]

[0114]

[0115] [Chemical Formula 4-3]

[0116]

[0117] [Chemical Formula 4-4]

[0118]

[0119] As an example of the present invention, the compound represented by Formula 5 may be selected from Formulas 5-1 to 5-4 below:

[0120] [Chemical Formula 5-1]

[0121]

[0122] [Chemical Formula 5-2]

[0123]

[0124] [Chemical Formula 5-3]

[0125]

[0126] [Chemical Formula 5-4]

[0127]

[0128] As an example of the present invention, the compound represented by Formula 6 may be selected from Formulas 6-1 to 6-4 below:

[0129] [Chemical Formula 6-1]

[0130]

[0131] [Chemical Formula 6-2]

[0132]

[0133] [Chemical Formula 6-3]

[0134]

[0135] [Chemical Formula 6-4]

[0136]

[0137] As an example of the present invention, the compound represented by Formula 7 may be selected from Formulas 7-1 to 7-16 below:

[0138] [Chemical Formula 7-1]

[0139]

[0140] [Chemical Formula 7-2]

[0141]

[0142] [Chemical Formula 7-3]

[0143]

[0144] [Chemical Formula 7-4]

[0145]

[0146] [Chemical Formula 7-5]

[0147]

[0148] [Chemical Formula 7-6]

[0149]

[0150] [Chemical Formula 7-7]

[0151]

[0152] [Chemical Formula 7-8]

[0153]

[0154] [Chemical Formula 7-9]

[0155]

[0156] [Chemical Formula 7-10]

[0157]

[0158] [Chemical Formula 7-11]

[0159]

[0160] [Chemical Formula 7-12]

[0161]

[0162] [Chemical Formula 7-13]

[0163]

[0164] [Chemical Formula 7-14]

[0165]

[0166] [Chemical Formula 7-15]

[0167]

[0168] [Chemical Formula 7-16]

[0169]

[0170] The present invention relates to a method for manufacturing a novel chitosan polymer compound according to the present invention.

[0171] According to one embodiment of the present invention, the method for preparing the novel chitosan polymer compound corresponds to the method for preparing the novel chitosan polymer compound, which is a compound represented by Chemical Formulas 1 to 7, and as an example of the present invention, the compound represented by Chemical Formulas 1 to 7 can be prepared according to the following reaction scheme.

[0172] According to one embodiment of the present invention, a compound represented by Chemical Formula 1-1 can be synthesized by reacting ethyl trifluoroacetate [CF3CO2C2H5] with a solution in which a chitosan polymer compound represented by Chemical Formula 1-a is dissolved in an ionic liquid, as shown in Reaction Scheme 1-1 below:

[0173] [Reaction Equation 1-1]

[0174]

[0175] (In the above reaction scheme 1-1, R1, R2, R3, R4, m, and n are each as defined in the above chemical formula 1.)

[0176] According to one embodiment of the present invention, a compound represented by Formula 1-2 can be synthesized by adding tritric anhydride [(CF3SO2)O] and triethylamine to a solution in which a chitosan polymer compound represented by Formula 1-a is dissolved in an ionic liquid, as shown in Reaction Scheme 1-2 below:

[0177] [Reaction Equation 1-2]

[0178]

[0179] (In the above reaction scheme 1-1, R1, R2, R3, R4, m, and n are each as defined in the above chemical formula 1.)

[0180]

[0181] According to one embodiment of the present invention, a compound represented by Chemical Formula 1-3 can be synthesized by reacting trifluoroacetic anhydride and 2,6-di-tertiary-butyl-4-methyl-pyridine with a solution in which a chitosan polymer compound represented by Chemical Formula 1-a is dissolved in an ionic liquid as shown in Reaction Scheme 1-3 below, and removing the pyridinium triplate by filtration:

[0182] [Reaction Equation 1-3]

[0183]

[0184] (In the above reaction schemes 1-3, R1, R2, R3, R4, m, and n are each as defined in the above chemical formula 1.)

[0185]

[0186] According to one embodiment of the present invention, as shown in the following reaction scheme 1-4, a compound represented by Formula 1-4 can be synthesized in a chloroform solvent in which tritric anhydride [(CF3SO2)O] and triethylamine are added to a solution in which a chitosan polymer compound represented by Formula 1-a is dissolved in an ionic liquid:

[0187] [Reaction Equation 1-4]

[0188]

[0189] (In the above reaction schemes 1-4, R1, R2, R3, R4, m, and n are each as defined in the above chemical formula 1.)

[0190]

[0191] According to one embodiment of the present invention, a compound represented by Formula 2-1 can be synthesized by adding an aqueous solution of sulfuric acid or sodium sulfate to a chitosan polymer compound represented by Formula 1-1 as shown in Reaction Scheme 2-1 below:

[0192] [Reaction Equation 2-1]

[0193]

[0194] (In the above reaction scheme 2-1, R1, R2, R3, R4, m, and n are each as defined in the above chemical formula 2.)

[0195] According to one embodiment of the present invention, a compound represented by Formula 2-2 can be synthesized by adding an aqueous solution of sulfuric acid or sodium sulfate to a chitosan polymer compound represented by Formula 1-2 as shown in Reaction Scheme 2-2 below:

[0196] [Reaction Equation 2-2]

[0197]

[0198] (In the above reaction scheme 2-2, R1, R2, R3, R4, m, and n are each as defined in the above chemical formula 2.)

[0199] According to one embodiment of the present invention, a compound represented by Formula 2-3 can be synthesized by adding an aqueous solution of sulfuric acid or sodium sulfate to a chitosan polymer compound represented by Formula 1-3 as shown in Reaction Scheme 2-3 below:

[0200] [Reaction Equation 2-3]

[0201]

[0202] (In the above reaction scheme 2-3, R1, R2, R3, R4, m, and n are each as defined in the above chemical formula 2.)

[0203] According to one embodiment of the present invention, a compound represented by Chemical Formula 2-4 can be synthesized by adding an aqueous solution of sulfuric acid or sodium sulfate to a chitosan polymer compound represented by Chemical Formula 1-4 as shown in Reaction Scheme 2-4 below:

[0204] [Reaction Equation 2-4]

[0205]

[0206] (In the above reaction scheme 2-4, R1, R2, R3, R4, m, and n are each as defined in the above chemical formula 2.)

[0207] According to one embodiment of the present invention, a compound represented by Formula 3-1 can be synthesized by adding an aqueous sodium phosphate solution to a chitosan polymer compound represented by Formula 1-1 as shown in Reaction Scheme 3-1 below:

[0208] [Reaction Equation 3-1]

[0209]

[0210] (In the above reaction scheme 3-1, R1, R2, R3, R4, m, and n are each as defined in the above chemical formula 3.)

[0211] According to one embodiment of the present invention, a compound represented by Formula 3-2 can be synthesized by adding an aqueous sodium phosphate solution to a chitosan polymer compound represented by Formula 1-2 as shown in Reaction Scheme 3-2 below:

[0212] [Reaction Equation 3-2]

[0213]

[0214] (In the above reaction scheme 3-2, R1, R2, R3, R4, m, and n are each as defined in the above chemical formula 3.)

[0215] According to one embodiment of the present invention, a compound represented by Formula 3-3 can be synthesized by adding an aqueous sodium phosphate solution to a chitosan polymer compound represented by Formula 1-3 as shown in Reaction Scheme 3-3 below:

[0216] [Reaction Equation 3-3]

[0217]

[0218] (In the above reaction scheme 3-3, R1, R2, R3, R4, m, and n are each as defined in the above chemical formula 3.)

[0219] According to one embodiment of the present invention, a compound represented by Formula 3-4 can be synthesized by adding an aqueous sodium phosphate solution to a chitosan polymer compound represented by Formula 1-4 as shown in Reaction Scheme 3-4 below:

[0220] [Reaction Equation 3-4]

[0221]

[0222] (In the above reaction schemes 3-4, R1, R2, R3, R4, m, and n are each as defined in the above chemical formula 3.)

[0223]

[0224] According to one embodiment of the present invention, a compound represented by Formula 4-1 can be synthesized by adding an aqueous sodium tripolyphosphate solution to a chitosan polymer compound represented by Formula 1-1 as shown in Reaction Scheme 4-1 below:

[0225] [Reaction Equation 4-1]

[0226]

[0227] (In the above reaction scheme 4-1, R1, R2, R3, R4, m, and n are each as defined in the above chemical formula 4.)

[0228]

[0229] According to one embodiment of the present invention, a compound represented by Formula 4-2 can be synthesized by adding an aqueous sodium tripolyphosphate solution to a chitosan polymer compound represented by Formula 1-6 as shown in Reaction Scheme 4-2 below:

[0230] [Reaction Equation 4-2]

[0231]

[0232] (In the above reaction scheme 4-2, R1, R2, R3, R4, m, and n are each as defined in the above chemical formula 4.)

[0233]

[0234] According to one embodiment of the present invention, a compound represented by Formula 4-3 can be synthesized by adding an aqueous sodium tripolyphosphate solution to a chitosan polymer compound represented by Formula 1-3 as shown in Reaction Scheme 4-3 below:

[0235] [Reaction Equation 4-3]

[0236]

[0237] (In the above reaction scheme 4-3, R1, R2, R3, R4, m, and n are each as defined in the above chemical formula 4.)

[0238]

[0239] According to one embodiment of the present invention, a compound represented by Formula 4-4 can be synthesized by adding an aqueous sodium tripolyphosphate solution to a chitosan polymer compound represented by Formula 1-4 as shown in Reaction Scheme 4-4 below:

[0240] [Reaction Equation 4-4]

[0241]

[0242] (In the above reaction scheme 4-4, R1, R2, R3, R4, m, and n are each as defined in the above chemical formula 4.)

[0243]

[0244] [Reaction Equation 5-1]

[0245] According to one embodiment of the present invention, a compound represented by Formula 5-1 can be synthesized by adding one or more citric acids selected from the group consisting of a chitosan polymer compound represented by Formula 1-1 and alginate, as shown in Reaction Scheme 5-1 below:

[0246]

[0247] (In the above reaction scheme 5-1, R1, R2, R3, R4, m, and n are each as defined in the above chemical formula 5.)

[0248]

[0249] [Reaction Equation 5-2]

[0250] According to one embodiment of the present invention, a compound represented by Formula 5-2 can be synthesized by adding one or more citric acids selected from the group consisting of a chitosan polymer compound represented by Formula 1-2 and alginate, as shown in Reaction Scheme 5-2 below:

[0251]

[0252] (In the above reaction scheme 5-2, R1, R2, R3, R4, m, and n are each as defined in the above chemical formula 5.)

[0253]

[0254] [Reaction Equation 5-3]

[0255] According to one embodiment of the present invention, a compound represented by Formula 5-3 can be synthesized by adding one or more citric acids selected from the group consisting of a chitosan polymer compound represented by Formula 1-3 and alginate, as shown in Reaction Scheme 5-3 below:

[0256]

[0257] (In the above reaction scheme 5-3, R1, R2, R3, R4, m, and n are each as defined in the above chemical formula 5.)

[0258]

[0259] [Reaction Equation 5-4]

[0260] According to one embodiment of the present invention, a compound represented by Chemical Formula 5-4 can be synthesized by adding one or more citric acids selected from the group consisting of a chitosan polymer compound represented by Chemical Formula 1-4 and alginate, as shown in Reaction Scheme 5-4 below:

[0261]

[0262] (In the above reaction scheme 5-4, R1, R2, R3, R4, m, and n are each as defined in the above chemical formula 5.)

[0263]

[0264] [Reaction Equation 6-1]

[0265] According to one embodiment of the present invention, as shown in the following reaction scheme 6-1, a compound represented by formula 6-1 can be synthesized by adding an acid catalyst, such as acetic acid, sulfuric acid, or perchloric acid, to glutaraldehyde in a chitosan polymer compound represented by formula 1-1:

[0266]

[0267] (In the above reaction scheme 6-1, R1, R2, R3, R4, m, and n are each as defined in the above chemical formula 6.)

[0268]

[0269] [Reaction Equation 6-2]

[0270] According to one embodiment of the present invention, as shown in the following reaction scheme 6-2, a compound represented by formula 6-2 can be synthesized by adding an acid catalyst, such as acetic acid, sulfuric acid, or perchloric acid, to glutaraldehyde in a chitosan polymer compound represented by formula 1-2:

[0271]

[0272] (In the above reaction scheme 6-2, R1, R2, R3, R4, m, and n are each as defined in the above chemical formula 6.)

[0273]

[0274] [Reaction Equation 6-3]

[0275] According to one embodiment of the present invention, as shown in the following reaction scheme 6-3, a compound represented by formula 6-3 can be synthesized by adding an acid catalyst, such as acetic acid, sulfuric acid, or perchloric acid, to glutaraldehyde in a chitosan polymer compound represented by formula 1-3:

[0276]

[0277] (In the above reaction scheme 6-3, R1, R2, R3, R4, m, and n are each as defined in the above chemical formula 6.)

[0278]

[0279] [Reaction Equation 6-4]

[0280] According to one embodiment of the present invention, as shown in the following reaction scheme 6-4, a compound represented by formula 6-4 can be synthesized by adding an acid catalyst, such as acetic acid, sulfuric acid, or perchloric acid, to glutaraldehyde in a chitosan polymer compound represented by formula 1-4:

[0281]

[0282] (In the above reaction scheme 6-4, R1, R2, R3, R4, m, and n are each as defined in the above chemical formula 6.)

[0283]

[0284] [Reaction Equation 7-1]

[0285] According to one embodiment of the present invention, a compound represented by Formula 7-1 can be synthesized by adding aniline to an aqueous solution in which a chitosan polymer compound represented by Formula 1-1 is dissolved in a hydrochloric acid solution, as shown in Reaction Scheme 7-1 below:

[0286]

[0287] (In the above reaction scheme 7-1, R1, R2, R3, R4, R5, R6, R7, R 8,, m, n, and o are each as defined in Chemical Formula 7 above.)

[0288]

[0289] [Reaction Equation 7-2]

[0290] According to one embodiment of the present invention, a compound represented by Formula 7-2 can be synthesized by adding aniline to an aqueous solution in which a chitosan polymer compound represented by Formula 1-2 is dissolved in a hydrochloric acid solution, as shown in Reaction Scheme 7-2 below:

[0291]

[0292] (In the above reaction scheme 7-2, R1, R2, R3, R4, R5, R6, R7, R 8,, m, n, and o are each as defined in Chemical Formula 7 above.)

[0293]

[0294] [Reaction Equation 7-3]

[0295] According to one embodiment of the present invention, a compound represented by Formula 7-3 can be synthesized by adding aniline to an aqueous solution in which a chitosan polymer compound represented by Formula 1-3 is dissolved in a hydrochloric acid solution, as shown in Reaction Scheme 7-3 below:

[0296]

[0297] (In the above reaction scheme 7-3, R1, R2, R3, R4, R5, R6, R7, R 8,, m, n, and o are each as defined in Chemical Formula 7 above.)

[0298]

[0299] [Reaction Equation 7-4]

[0300] According to one embodiment of the present invention, a compound represented by Chemical Formula 7-4 can be synthesized by adding aniline to an aqueous solution in which a chitosan polymer compound represented by Chemical Formula 1-4 is dissolved in a hydrochloric acid solution, as shown in Reaction Scheme 7-4 below:

[0301]

[0302] (In the above reaction scheme 7-4, R1, R2, R3, R4, R5, R6, R7, R 8,,m, n, and o are each as defined in Chemical Formula 7 above.)

[0303]

[0304] [Reaction Equation 7-5]

[0305] According to one embodiment of the present invention, a compound represented by Formula 7-5 can be synthesized by adding aniline and 2,2,2-trifluoro-N-phenyl-acetamide to an aqueous solution in which a chitosan polymer compound represented by Formula 1-1 is dissolved in a hydrochloric acid solution, as shown in Reaction Scheme 7-5 below:

[0306]

[0307] (In the above reaction scheme 7-5, R1, R2, R3, R4, R5, R6, R7, R 8,, m, n, and o are each as defined in Chemical Formula 7 above.)

[0308]

[0309] [Reaction Equation 7-6]

[0310] According to one embodiment of the present invention, a compound represented by Chemical Formula 7-6 can be synthesized by adding aniline and C,C,C-trifluoro-N-phenyl-methanesulfonamide to an aqueous solution in which a chitosan polymer compound represented by Chemical Formula 1-2 is dissolved in a hydrochloric acid solution, as shown in Reaction Scheme 7-6 below:

[0311]

[0312] (In the above reaction scheme 7-6, R1, R2, R3, R4, R5, R6, R7, R 8,, m, n, and o are each as defined in Chemical Formula 7 above.)

[0313]

[0314] [Reaction Equation 7-7]

[0315] According to one embodiment of the present invention, a compound represented by Formula 7-7 can be synthesized by adding aniline and 2,2,2-trifluoro-N-phenyl-acetamide to an aqueous solution in which a chitosan polymer compound represented by Formula 1-3 is dissolved in a hydrochloric acid solution, as shown in Reaction Scheme 7-7 below:

[0316]

[0317] (In the above reaction scheme 7-7, R1, R2, R3, R4, R5, R6, R7, R 8,, m, n, and o are each as defined in Chemical Formula 7 above.)

[0318]

[0319] [Reaction Equation 7-8]

[0320] According to one embodiment of the present invention, a compound represented by Chemical Formula 7-8 can be synthesized by adding aniline and C,C,C-trifluoro-N-phenyl-methanesulfonamide to an aqueous solution in which a chitosan polymer compound represented by Chemical Formula 1-4 is dissolved in a hydrochloric acid solution, as shown in Reaction Scheme 7-8 below:

[0321]

[0322] (In the above reaction schemes 7-8, R1, R2, R3, R4, R5, R6, R7, R 8,, m, n, and o are each as defined in Chemical Formula 7 above.)

[0323]

[0324] [Reaction Equation 7-9]

[0325] According to one embodiment of the present invention, a compound represented by Formula 7-9 can be synthesized by adding anthranilic acid to an aqueous solution in which a chitosan polymer compound represented by Formula 1-1 is dissolved in a hydrochloric acid solution, as shown in Reaction Scheme 7-9 below:

[0326]

[0327] (In the above reaction scheme 7-9, R1, R2, R3, R4, R5, R6, R7, R 8,, m, n, and o are each as defined in Chemical Formula 7 above.)

[0328]

[0329] [Reaction Equation 7-10]

[0330] According to one embodiment of the present invention, a compound represented by Formula 7-10 can be synthesized by adding anthranilic acid to an aqueous solution in which a chitosan polymer compound represented by Formula 1-2 is dissolved in a hydrochloric acid solution, as shown in Reaction Scheme 7-10 below:

[0331]

[0332] (In the above reaction schemes 7-10, R1, R2, R3, R4, R5, R6, R7, R 8,, m, n, and o are each as defined in Chemical Formula 7 above.)

[0333]

[0334] [Reaction Equation 7-11]

[0335] According to one embodiment of the present invention, a compound represented by Formula 7-11 can be synthesized by adding anthranilic acid to an aqueous solution in which a chitosan polymer compound represented by Formula 1-3 is dissolved in a hydrochloric acid solution, as shown in Reaction Scheme 7-11 below:

[0336]

[0337] (In the above reaction scheme 7-11, R1, R2, R3, R4, R5, R6, R7, R 8,, m, n, and o are each as defined in Chemical Formula 7 above.)

[0338]

[0339] [Reaction Equation 7-12]

[0340] According to one embodiment of the present invention, a compound represented by Chemical Formula 7-12 can be synthesized by adding anthranilic acid to an aqueous solution in which a chitosan polymer compound represented by Chemical Formula 1-4 is dissolved in a hydrochloric acid solution, as shown in Reaction Scheme 7-12 below:

[0341]

[0342] (In the above reaction scheme 7-12, R1, R2, R3, R4, R5, R6, R7, R 8,, m, n, and o are each as defined in Chemical Formula 7 above.)

[0343]

[0344] [Reaction Equation 7-13]

[0345] According to one embodiment of the present invention, a compound represented by Formula 7-13 can be synthesized by adding anthranilic acid and 2-(2,2,2-trifluoro-acetylamino)-benzoic acid to an aqueous solution in which a chitosan polymer compound represented by Formula 1-1 is dissolved in a hydrochloric acid solution, as shown in Reaction Scheme 7-13 below:

[0346]

[0347] (In the above reaction scheme 7-13, R1, R2, R3, R4, R5, R6, R7, R 8,, m, n, and o are each as defined in Chemical Formula 7 above.)

[0348]

[0349] [Reaction Equation 7-14]

[0350] According to one embodiment of the present invention, a compound represented by Chemical Formula 7-14 can be synthesized by adding anthranilic acid and 2-trifluoromethanesulfonylamino-benzoic acid to an aqueous solution in which a chitosan polymer compound represented by Chemical Formula 1-2 is dissolved in a hydrochloric acid solution, as shown in Reaction Scheme 7-14 below:

[0351]

[0352] (In the above reaction scheme 7-14, R1, R2, R3, R4, R5, R6, R7, R 8,, m, n, and o are each as defined in Chemical Formula 7 above.)

[0353]

[0354] [Reaction Equation 7-15]

[0355] According to one embodiment of the present invention, a compound represented by Chemical Formula 7-15 can be synthesized by adding anthranilic acid and 2-(2,2,2-trifluoro-acetylamino)-benzoic acid to an aqueous solution in which a chitosan polymer compound represented by Chemical Formula 1-3 is dissolved in a hydrochloric acid solution, as shown in Reaction Scheme 7-15 below:

[0356]

[0357] (In the above reaction scheme 7-15, R1, R2, R3, R4, R5, R6, R7, R 8,, m, n, and o are each as defined in Chemical Formula 7 above.)

[0358]

[0359] [Reaction Equation 7-16]

[0360] According to one embodiment of the present invention, a compound represented by Chemical Formula 7-16 can be synthesized by adding anthranilic acid and 2-trifluoromethanesulfonylamino-benzoic acid to an aqueous solution in which a chitosan polymer compound represented by Chemical Formula 1-4 is dissolved in a hydrochloric acid solution, as shown in Reaction Scheme 7-16 below:

[0361]

[0362] (In the above reaction scheme 7-16, R1, R2, R3, R4, R5, R6, R7, R 8,, m, n, and o are each as defined in Chemical Formula 7 above.)

[0363]

[0364] According to one embodiment of the present invention, in order to obtain a final product according to a chemical structural design, the starting materials, catalyst, solvent, reaction conditions, reaction mechanism, and post-treatment processes (reactant separation, filtration, crystallization, washing, etc.) may appropriately utilize or replace methods known in the art of the present invention. For example, the process may be carried out at a reaction temperature of -10°C or higher; 0°C or higher; room temperature or higher; 40°C or higher; 50°C or higher; 80°C or higher; or 100°C or higher in a single solvent or mixed solvent such as water, methanol, isopropanol, ethanol, methylene chloride, dichloromethane, acetonitrile, tetrahydrofuran, methyl-tert-butyl ether, chloroform, DMF, and N,N-dimethylacetamide. For example, the reaction temperature may be appropriately selected according to the reflux conditions of the reaction mixture. In addition, catalysts such as platinum catalysts, basic substances (triethylamine, diisopropylethylamine, pyridine, etc.) may be further added.

[0365] The binder serves to maintain electrode integrity and adhesion to the current collector. Like electrically conductive materials and electrolytes, the binder is not electrochemically active. Therefore, the less binder is added, the more electrochemically active material can be added, thereby increasing energy density and cell capacity. Binders that are soluble in aqueous solutions are substantially soluble in water-based solvents and may include carboxymethyl cellulose or “CMC” and styrene-butadiene rubber or “SBR”, similar water-soluble binders, and mixtures thereof.

[0366] In addition to SBR and CMC, other binders that can be dispersed or dissolved in aqueous solutions include polytetrafluoroethylene (PTFE), ethylene propylene diene monomer (EPDM) rubber and other rubbers, poly-polystyrene sulfonate (PEDOT-PSS), polyacrylic acid (PAA), poly(methyl acrylate) (PMA), poly(vinyl alcohol) (PVA), poly(vinyl acetate) (PVAc), polyacrylonitrile (PAN), polyisoprene (PIpr), polyaniline (PANi), polyethylene (PE), polyimide (PI), polystyrene (PS), polyurethane, polyvinyl butyral (PVB), polyvinyl pyrrolidone (PVP), and modifications and combinations thereof. Additional natural binders dispersed or soluble in aqueous solutions include amylose, casein, cyclodextrine (carbonyl-beta), cellulose (natural), starch, alginate, chitosan, gum (e.g., gellan, guar, xanthan, karaya, tara, tragacanth, and arabic), agar, pectin, and carrageenan.

[0367] In the present invention, chemical and / or physical modifications may be made to these natural binders. A combination of one or more natural and / or modified binders may be used. The binder may be dispersed in an aqueous solution so that binder microparticles are dispersed to maintain the cohesiveness of the electrode and / or electrical conductivity between the electrode and individual electrode leads. Additionally, a binder that is soluble in an aqueous solution may be used in the present invention. The present invention features a crosslinkable siloxane-based polymer electrolyte having a binder that can be crosslinked as needed, e.g., a chitosan-based polymer compound, and the crosslinked binder mixture may include tertiary and other additional binders to provide desired mechanical advantages. In other embodiments, the present invention features a binder that is soluble and well dispersed in an aqueous solvent and / or a binder that is partially soluble or not dispersed. The process for manufacturing the electrochemical cell also varies depending on the configuration of the cell, other components or elements of the cell, and the cell size. The battery chemical active material needs to be ionically connected with the solid polymer electrolyte and electrically connected with the electrically conductive material.

[0368] The present disclosure relates to a composition comprising chitosan and at least one phosphate or its conjugated acid for general use as a binder for battery electrodes, a battery comprising the same, and a method for manufacturing the same. The scope of the present disclosure is not limited by any one of the specific embodiments described herein. The following embodiments are provided merely for illustrative purposes.

[0369] Although binders account for only 2–5% of the mass in typical commercial electrode configurations, binder materials are one of the most critical electrode components for improved cell performance, particularly regarding cycle life. Without binders, the active material loses contact with the current collector, resulting in a loss of capacity.

[0370] The properties of chitosan are influenced by several parameters, such as molecular weight (10,000–1,000,000 Da) and the degree of deacetylation (representing the ratio of 2-amino-2-deoxy-d-glucopyranose to 2-acetamido-2-deoxy-d-glucopyranose structural units of chitosan). The degree of deacetylation of the chitosan used in the binder described herein may be in the range of 0% to 100%. In certain embodiments, the degree of deacetylation of the chitosan used in the binder described herein is greater than 1%, greater than 5%, greater than 10%, greater than 20%, greater than 30%, greater than 40%, greater than 50%, greater than 60%, greater than 70%, greater than 80%, greater than 90%, greater than 95%, greater than 97%, greater than 98%, greater than 99%, or greater than 99.9%. In certain embodiments, the degree of deacetylation of the chitosan used in the binder described herein is 50-100%, 60-99%, 65-99%, 65-99%, 70-99%, 75-99%, or 75-95%. In certain embodiments, the degree of deacetylation of the chitosan used in the binder described herein is between 75-95%.

[0371] Chitosan may have a molecular weight of 10,000 to 1,000,000 Da. In certain embodiments, chitosan may have a molecular weight of 10,000 to 500,000; 20,000 to 500,000; 30,000 to 500,000; 40,000 to 500,000; 40,000 to 450,000; or 40,000 to 400,000 Da. In certain embodiments, chitosan may be low molecular weight (molecular weight 50,000 to 190,000 Da), medium molecular weight chitosan (molecular weight 190,000 to 310,000 Da); or high molecular weight chitosan (molecular weight ~310,000 to >375,000 Da).

[0372] The binders and binder compositions provided herein utilize the unique properties of compositions comprising chitosan and phosphate or their conjugated acids. The binders and binder compositions described herein may be used in connection with any type of anode or cathode known in the art. Accordingly, the following examples should not be construed as limiting the use of the binders and binder compositions described herein.

[0373] Chitosan can exist as a polycationic polymer well known for its chelating properties. Therefore, interactions with negatively charged components, such as metal phosphate salts, can lead to the formation of network ionically phosphate crosslinked chitosan chains. Ionic interactions between the negative charge of the phosphate and the positively charged group of chitosan are considered to be the major molecular interactions within the crosslinked network. The formation of network ionically phosphate crosslinked chitosan chains can be prepared by combining cationic chitosan with at least one phosphate; or alternatively, by combining neutral chitosan with the conjugated acid of at least one phosphate. Consequently, the binder composition considered herein comprises a binder composition comprising chitosan and at least one phosphate or its conjugated acid.

[0374] The binder provided herein may comprise chitosan and at least one phosphate selected from the group consisting of metal orthophosphates, metal pyrophosphates, and metal polyphosphates. In certain embodiments, the binder has one, two, three, four or more different types of phosphates.

[0375] Polymetal phosphate salts suitable for use in the binders described herein include, but are not limited to, linear polymetal phosphate salts, mechametal phosphate salts, metametal phosphate salts, and branched polymetal phosphate salts. Exemplary polymetal phosphate salts include, but are not limited to, triphosphate, tetraphosphate, pentaphosphate, trimetaphosphate, tetrametaphosphate, etc. At least one phosphate may include any metal cation. Exemplary metal cations include one or more cations selected from Group 1 and Group 2 of the periodic table. In certain embodiments, at least one phosphate is Li + , Na + , K + , Mg 2+ and Ca 2+ It may include one or more metal cations selected from the group consisting of. In certain embodiments, at least one phosphate is sodium orthophosphate, sodium pyrophosphate, or sodium polyphosphate. In certain embodiments, at least one phosphate is sodium tripolyphosphate. The binder may also include chitosan and at least one phosphate conjugated acid selected from the group consisting of orthophosphate, pyrophosphate, and polyphosphate conjugated acids.

[0376] Conjugate acids of orthophosphates, pyrophosphates, and polyphosphates suitable for use in the binders described herein include, but are not limited to, linear polyphosphates, metaphosphates, and branched polyphosphates. Exemplary polyphosphates include, but are not limited to, triphosphates, tetraphosphates, pentaphosphates, trimetaphosphates, tetrametaphosphates, etc. In certain embodiments, the conjugate acid of the phosphate is polyphosphate (CAS No.: 8017-16-1).

[0377] The conjugate acids of orthophosphates, pyrophosphates, and polyphosphates may contain one or more ionizable protons and thus may exist in one or more conjugate acid protonation states. When a binder composition comprises a conjugate acid of an orthophosphate, pyrophosphate, or polyphosphate, the conjugate acid may be any possible protonation state of the phosphate described herein or a combination thereof. For example, the conjugate acid of PO43- (orthophosphate) comprises HPO42-, H2PO4-, and H3PO4; and the conjugate acid of P3O105- (tripolyphosphate) comprises HP3O104-, H2P3O103-, H3P3O102-, H4P3O101-, and H5P3O10. The anionic conjugate acid of the phosphate may comprise any one or more metal cations described herein.

[0378] The binder may contain at least one phosphate or its conjugated acid in a mass ratio of 1:1 to 1:10,000. In certain embodiments, the binder comprises at least one phosphate and chitosan in a mass ratio of 1:1 to 1:10,000; 1:1 to 1:5,000; 1:1 to 1:1,000; 1:1 to 1:500; 1:1 to 1:250; 1:1 to 1:100; 1:1 to 1:20; 1:1 to 1:10; 1:5 to 1:10; 1:6 to 1:10; 1:7 to 1:10; 1:7 to 1:9; or 1:8 to 1:9. In certain embodiments, the binder comprises less than 1 weight part of at least one phosphate for every 4 weight parts of chitosan. In certain embodiments, the binder comprises less than 1 part by weight of at least one phosphate with respect to 5 parts by weight of chitosan; less than 1 part by weight of at least one phosphate with respect to 6 parts by weight of chitosan; less than 1 part by weight of at least one phosphate with respect to 7 parts by weight of chitosan; less than 1 part by weight of at least one phosphate with respect to 8 parts by weight of chitosan; or less than 1 part by weight of at least one phosphate with respect to 9 parts by weight of chitosan. In the example below, the binder comprises sodium tripolyphosphate and chitosan in a mass ratio of 1:8.3.

[0379] Chitosan is relatively insoluble in water and most organic and alkaline solvents. However, chitosan is soluble in solvents containing dilute organic acids such as acetic acid, formic acid, lactic acid, oxalic acid, benzoic acid, and lactic acid. A binder composition comprising the binder described herein and optionally a solvent containing an organic acid is provided. The solvent may be an aqueous solvent, a polar organic solvent, or a mixture thereof. Suitable polar organic solvents include, but are not limited to, alcohols, alkyl halides, dialkyl formamides, dialkyl ketones, dialkyl sulfoxides, tertiary amides, and combinations thereof. Exemplary polar organic solvents include, but are not limited to, methanol, ethanol, isopropanol, dimethyl formamide (DMF), dimethyl sulfoxide (DMSO), dimethyl acetamide (DMA), acetone, methyl ethyl ketone, and N-methyl-2-pyrrolidone. The organic acid may be acetic acid, propionic acid, formic acid, lactic acid, oxalic acid, succinic acid, tartaric acid, malic acid, benzoic acid, methylsulfonic acid, phenylsulfonic acid, toluenesulfonic acid, or a combination thereof. The organic acid may be present in the solvent at a concentration of about 0.1-5% v / v. In certain embodiments, the organic acid is acetic acid. When a conjugated acid of a phosphate is used, it may be used to solubilize chitosan in a solvent such as water instead of the organic acid.

[0380] The binder composition may have a solid content of 0.1% wt / wt or more, wherein the solid content is determined according to the following formula: (weight of at least one phosphate + weight of chitosan) / (weight of solvent + weight of at least one phosphate + weight of chitosan). In certain embodiments, the binder has a solid content of 0.5% wt / wt, 1.0% wt / wt, 1.5% wt / wt, 2.0% wt / wt or more. In certain embodiments, the binder composition has a solid content between 0.1-20% wt / wt, 0.1-15% wt / wt, 0.1-10% wt / wt, 1-10% wt / wt, 1-5% wt / wt, 1-4% wt / wt, 1-3% wt / wt, or 1-1.5% wt / wt.

[0381] In certain embodiments, the binder composition comprises sodium tripolyphosphate and chitosan in an aqueous solution containing acetic acid.

[0382] In addition, an anode slurry comprising a binder composition described in this specification, at least one conductive additive, and at least one anode active material is provided in this specification.

[0383] The anode active material may be any anode active material known in the industry.

[0384] In certain embodiments, the anode active material comprises a metal selected from groups IA, IIA, IIB, and IVB of the periodic table of elements and a compound capable of forming intermetallic compounds and alloys with a metal selected from groups IA, IIA, IIIB, and IVB of the periodic table of elements. Examples of such anode active materials include lithium, sodium, potassium, and their alloys, and compounds capable of forming intermetallic compounds and alloys with lithium, sodium, and potassium. Examples of suitable alloys include, but are not limited to, Li-Si, Li-Al, Li-B, and Li-Si-B. Examples of suitable intermetallic compounds include, but are not limited to, intermetallic compounds comprising or composed of two or more components selected from the group consisting of Li, Ti, Cu, Sb, Mn, Al, Si, Pb, Sn, In, Bi, Ag, Ba, Ca, Hg, Pd, Pt, Te, Zn, and La. Other examples of suitable intermetallic compounds include, but are not limited to, intermetallic compounds comprising lithium metal and one or more components selected from the group consisting of Ti, Cu, Sb, Mn, Al, Si, Pb, Sn, In, Bi, Ag, Ba, Ca, Hg, Pd, Pt, Te, Zn, and La. Other suitable anode active materials include lithium titanium oxide such as Li4Ti5O12, silica alloys, and mixtures of said anode active materials. The anode active material may be a graphite-based material such as natural graphite, artificial graphite, coke, and carbon fiber; a compound containing at least one element such as Al, Si, Sn, Ag, Bi, Mg, Zn, In, Ge, Pb, and Ti that can be alloyed with lithium, sodium, or potassium; a composite composed of a graphite-based material and carbon, a compound containing at least one element that can be alloyed with lithium, sodium, or potassium; or a lithium-containing nitride; and combinations thereof.

[0385] In certain embodiments, the anode active material is silicon nanoparticles, single-crystal silicon nanoparticles, single-crystal silicon nanoflakes, silicon powder, silicon oxide, silicon oxide nanoparticles, SiOx particles (where x is 0.1 to 1.9), silicon nanotubes, silicon nanowires, tin nanopowder, tin oxide nanopowder, and combinations thereof.

[0386] The conductive additive present in the anode and / or cathode may be a carbon conductive additive, a polymer conductive additive, a metal conductive additive, or a combination thereof. Suitable carbon conductive additives include, but are not limited to, natural graphite, synthetic graphite, carbon fiber, carbon nanofiber, carbon black, acetylene black, Ketjen black, carbon nanotubes, graphene, graphene oxide, and combinations thereof. In certain embodiments, the conductive additive is carbon black nanopowder, carbon nanoparticles, double-walled carbon nanotube, 3D graphene foam, graphene monolayer, graphene multilayer, graphene nanoplatelet, graphene oxide monolayer, graphene oxide paper, graphene oxide thin film, graphene nanofiber, graphite powder, graphite rod, and combinations thereof; It is a conductive metal additive selected from the group consisting of polyacetylene, polypyrrole, poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS), polyaniline, polyparaphenylene vinylene, polyisothianaphthalene, polyparaphenylene sulfide, polyparaphenylene and combinations thereof; or copper, nickel, aluminum, silver, etc.

[0387] Generally, all types of conductive additives (including metal fibers, metal powders, graphite powders, and carbon nanomaterials) can be used; however, compared to metal fibers or metal powders, carbon nanomaterials possess superior properties such as low weight, high chemical inertia, and a high specific surface area. Therefore, the most widely used conductive additives in lithium-ion batteries are carbon nanomaterials, such as carbon black, Super P, acetylene black, carbon nanofibers, and carbon nanotubes. An ideal electrode for a lithium-ion battery must possess high electronic and ionic conductivity. Electronic conductivity depends on the electronic conductivity of the electrode. Ionic conductivity depends on ion diffusion, which is closely related to the pores of the cathode. Porous structures, particularly mesoporous structures, can absorb and retain the electrolyte solution, enabling close contact between lithium ions and the electrode active material.

[0388] Since the first CCF, produced by carbonizing cotton and bamboo, was used as a light bulb filament by Thomas Edison in 1879, it has made tremendous progress in basic scientific research and practical applications. As one of the most important components of CCF and CNF, it has been applied as a promising material in many fields such as energy conversion and storage, reinforcement of composites, and self-sensing devices.

[0389] There are some differences between CCF and CNF. The first and most obvious difference is their size. CCF can have a diameter of several micrometers, whereas CNF can have a diameter of 50–200 nm. Aside from the diameter, the structure of CNF is clearly different from conventional carbon fibers. CNF can be manufactured primarily through two approaches: catalytically vapor deposition growth and electrospinning.

[0390] One of the most important characteristics of CNF composites is electrical conductivity. When CNF composites are applied as electrodes for electrical devices, sensors, electromagnetic shielding, or batteries or supercapacitors, electrical conductivity must always be considered a top priority.

[0391] Compared to single-conducting additives, multi-conducting additives can possess the advantages of two or more conductors, which can lead to synergistic effects. Therefore, multi-conducting additives generally demonstrate slight superiority over single-conducting additives. For example, carbon black (CB) adheres to the surface of the cathode active material to increase its conductivity, while CNF binds to the cathode active material. Thus, multi-conducting additives generally show slight superiority over single-conducting additives. Micro-sized graphite disperses easily with the cathode active material, but it may not form an excellent conductive network when used in small quantities. The addition of nano-sized super-P, etc., forms a good conductive network, improving cycle life and enabling the attainment of cathodes with higher discharge capacity.

[0392] As discussed, fibrous carbon can easily form a conductive network. However, fibrous carbon may have fewer contact points with the cathode active material compared to particulate carbon. If particulate carbon and fibrous carbon are mixed together to form a multi-conductive additive, the advantages of both types of conductors can be obtained.

[0393] A binder is important for maintaining the particles in electrical contact and for assembling high-quality electrodes regardless of particle size. An ideal binder must provide the best elasticity to the anode complex and fully accommodate the expansion of the active material during the lithiation / delithiation process, as shown in Fig. 2.

[0394] An anode slurry can be prepared by combining the binder composition described herein, at least one conductive additive, and at least one anode active material to form an anode slurry.

[0395] The particle size of the anode slurry can be optionally reduced using any method known in the industry.

[0396] There are various known methods for controlling the particle size of a material, including reduction by grinding or de-aggregation through milling and / or sieving. Exemplary methods for particle reduction include, but are not limited to, jet milling, hammer milling, compression milling, and tumble milling processes (e.g., ball milling). Particle size control parameters for these processes are well understood by those skilled in the art. For example, particle size reduction achieved in the jet milling process is controlled by adjusting a number of parameters, the main parameters being mill pressure and feed rate. In the hammer milling process, particle size reduction is controlled by the feed rate, hammer speed, and the size of the opening of the grate / screen at the outlet. In the compression milling process, particle size reduction is controlled by the feed rate applied to the material and the amount of compression (e.g., the amount of force applied to the compression roller).

[0397] In certain embodiments, the anode slurry is ball-milled to reduce the particle size of the slurry.

[0398] The anode slurry can be optionally freeze-dried to form a freeze-dried anode material, which can improve anode cycle stability by forming cavities (voids) within the formed freeze-dried anode material. Furthermore, freeze-drying can advantageously improve rate capability because the more porous the structure of the freeze-dried anode material, the greater the ion transport at the electrode and the improved surface area, thereby accelerating the charge transfer reaction rate.

[0399] Freeze-drying of anode slurries can result in anode materials having a much larger surface area than non-freeze-dried anode materials. For example, freeze-dried anode materials have a surface area of ​​20–40 m² 2 / g, 20-35 m 2 / g, 25-35 m 2 / g or 25-30 m 2 It can have an average surface area of ​​ / g. Likewise, the freeze-dried total pore volume is also improved to 0.200 to 0.250 cm². 3 / g, 0.200 to 0.240 cm 3 / g, 0.200 to 0.230 cm 3 / g, 0.210 to 0.230 cm 3 / g or 0.220 to 0.230 cm 3 It may be in the range of / g. The freeze-dried anode material may have an average pore diameter between 30-40 nm, 32-38 nm, or 32-36 nm.

[0400] To improve the freeze-dried anode material for the cathode current collector, a slurry containing the freeze-dried anode material can be prepared by adding a solvent to the freeze-dried anode material. A solvent useful for preparing a binder composition can also be used to prepare a slurry containing the freeze-dried anode material.

[0401] An anode slurry can be applied onto a cathode current collector and heated, and then further heat-treated in a vacuum to form an electrode active material layer. In some embodiments, depending on the viscosity of the slurry, the coating may be performed using one or more methods selected from the group consisting of screen printing, spray coating, coating using a doctor blade, gravure coating, dip coating, silk screen, painting, and coating using a slot die.

[0402] The negative current collector may be any material that is conductive without causing chemical changes in the lithium battery, such as copper, stainless steel, aluminum, nickel, titanium, sintered carbon, or copper or stainless steel or aluminum-cadmium alloy surface-treated with nickel, titanium, silver, etc. Additional exemplary negative current collectors include, but are not limited to, copper foil, copper mesh foil, copper foam sheet, nickel foam sheet, nickel mesh foil, and nickel foil. In some embodiments, the negative current collector may be any of various forms including film, sheet, foil, net, porous structure, foam, and non-woven fabric.

[0403] In addition, a cathode slurry comprising a binder composition described in this specification, at least one conductive additive, and at least one cathode active material is provided in this specification.

[0404] Suitable cathode active materials include, but are not limited to, lithium transition metal oxides. Lithium transition metal oxides may include one or more transition metals and oxygen in addition to lithium, or may be composed of lithium, one or more transition metals, and oxygen. If the lithium transition metal oxide includes cobalt as a transition metal, the lithium transition metal oxide may include more than one transition metal. In some embodiments, the lithium transition metal oxide excludes cobalt. The transition metal of the lithium transition metal oxide may include or be composed of one or more elements selected from the group consisting of Li, Al, Mg, Ti, B, Ga, Si, Mn, Zn, Mo, Nb, V, Ag, Ni, and Co. Suitable lithium transition metal oxides include Li x VO y , LiCoO2, LiNiO2, LiNi 1-x Co y Me zO2, LiMn 0.5 Ni 0.5 O2, LiMn 1 / 3 Co 1 / 3 Ni 1 / 3 O2, LiFeO2, Li z M yy Me is one or more transition metals selected from Li, Al, Mg, Ti, B, Ga, Si, Mn, Zn, Mo, Nb, V, Ag and combinations thereof, and M is one or more transition metals such as Mn, Ti, Ni, Co, Cu, Mg, Zn, V and combinations thereof, including but not limited to O4.

[0405] In some examples, 0 before the initial charge of the battery <x<1 및 / 또는 배터리의 초기 충전 전 0<y<1 및 / 또는 배터리의 초기 충전 전 x≥0 및 / 또는 1-x+y+z=1 및 / 또는 배터리의 초기 충전 전 0.8<z<1.5 및 / 또는 배터리의 초기 충전 전 1.5<yy<2.5 이다.

[0406] Additional examples of cathode active materials are LiCoO2, LiNiO2, and LiNi 1-x Co y Me z O2, LiMn 0.5 Ni 0.5 O2, LiMn (1 / 3) Co (1 / 3) Ni (1 / 3) O2 and LiNiCo y Al z It is O2.

[0407] A cathode slurry can be prepared by combining a binder composition described in this specification, at least one conductive additive, and at least one cathode active material to form a cathode slurry.

[0408] In certain embodiments, the cathode slurry undergoes ball milling to reduce the particle size of the slurry.

[0409] The cathode slurry can be optionally freeze-dried to form a freeze-dried cathode material.

[0410] To improve the application of freeze-dried cathode material to a positive current collector, a slurry containing freeze-dried cathode material can be prepared by adding a solvent to the freeze-dried cathode material. A solvent useful for preparing a binder composition can also be used to prepare a slurry containing freeze-dried cathode material.

[0411] A cathode slurry can be applied onto an anode current collector and heated, and then further heat-treated in a vacuum to form a layer of electrode active material. In some embodiments, depending on the viscosity of the slurry, the coating may be performed using one or more methods selected from the group consisting of screen printing, spray coating, coating using a doctor blade, gravure coating, dip coating, silk screen, painting, and coating using a slot die.

[0412] The positive current collector may be any material having high conductivity that does not cause chemical changes in the lithium battery, such as stainless steel, aluminum, nickel, titanium, sintered carbon, or aluminum or stainless steel surface-treated with carbon, nickel, titanium, silver, etc. In some embodiments, the positive current collector may have fine irregularities on its surface to improve adhesion strength to the positive active material. The positive current collector may be any of various forms including films, sheets, foils, nets, porous structures, foams, and nonwoven fabrics.

[0413] In certain embodiments, the apparatus comprises an anode; a cathode disposed opposite the anode; and an electrolyte disposed between the anode and the cathode, wherein at least one of the anode and the cathode comprises a binder or binder composition as described herein.

[0414] In certain embodiments, a lithium battery is provided herein comprising: a positive current collector; a positive electrode; a negative current collector; a negative electrode disposed opposite to the positive electrode; a separator substrate disposed between the positive electrode and the negative electrode; and an electrolyte disposed between the separator substrate and the positive electrode and between the separator substrate and the negative electrode, wherein at least one of the positive electrode and the negative electrode comprises a binder or binder composition as described herein.

[0415]

[0416] The present invention will be explained in more detail below through examples and comparative examples. However, the following examples are merely illustrative of the present invention, and the scope of the present invention is not limited to the following examples.

[0417] [Example 1]

[0418] [Reaction Scheme 1-1] Synthesis of Chitosan-g-(2,2,2-trifluoroacetamide) (Compound 1-1)

[0419]

[0420] Chitosan (34.2 g, 157.5 mmol) and ethyl trifluoroacetate (2.5 g, 17.6 mmol) were added dropwise to 40 ml of chloroform under a nitrogen atmosphere. The solution was stirred at room temperature for 4 hours, and volatile substances were removed under reduced pressure. Chloroform was removed under vacuum to obtain the product chitosan-g-(2,2,2-trifluoroacetamide) (compound 1-1).

[0421] 1 H NMR (300MHz, CDCl3): ppm 2.08(m, 1H), 3.24 (m, 6H), 3.50(m, 2H), 3.56(m, 1H), 3.66 (m, 4H), 4.01(m, 1H), 4.30(m, 1H), 7.38(m, 1H); 13 C NMR (300MHz, CDCl3): 8.0, 26.1, 44.4, 52.0, 54.2, 63.6, 71.6, 75.6, 125.6, 170.6; 19F NMR (CDCl3): ppm -77.3 (s)

[0422]

[0423] [Reaction Scheme 1-2] Synthesis of Chitosan-g-(C,C,C-trifluoro-methanesulfonamide) (Compound 1-2)

[0424]

[0425] Triflic anhydride (5.0 g, 18 mmol) was added dropwise under a nitrogen atmosphere to a mixture of chitosan (34.2 g, 157.5 mmol) and triethylamine (2.0 g, 20 mmol) mixed in 40 ml of chloroform at -40°C. The solution was stirred at room temperature for 4 hours, and volatile substances were removed under reduced pressure. The remaining viscous liquid was dissolved in 30 ml of 4 M NaOH, washed three times with 25 ml of chloroform, and the aqueous component was neutralized with HCl, followed by washing three more times with 30 ml of chloroform. Subsequently, the organic extract was dried with anhydrous MgSO4 and filtered. Chloroform was removed under vacuum to obtain the product chitosan-g-(C,C,C-trifluoro-methanesulfonamide) (Compound 1-2).

[0426] 1 H NMR (300MHz, CDCl3): ppm 2.08(m, 1H), 3.04(m, 1H), 3.17(m, 1H), 3.24 (m, 6H), 3.50(m, 2H), 3.66 (m, 2H), 3.91(m, 2H), 7.38(m, 1H); 13 C NMR (300MHz, CDCl3): 8.0, 26.1, 42.4, 52.0, 54.2, 63.6, 71.6, 72.7, 75.6, 149.7; 19 F NMR (CDCl3): ppm -77.5 (s)

[0427]

[0428] [Reaction Scheme 1-3] Synthesis of Chitosan-g-(2,2,2-trifluoro-N-trifluoroacetyl-acetamide) (Compound 1-3)

[0429]

[0430] Chitosan (34.2 g, 157.5 mmol) and ethyl trifluoroacetate (5 g, 35.2 mmol) were added dropwise to 40 ml of chloroform under a nitrogen atmosphere. The solution was stirred at room temperature for 4 hours, and volatile substances were removed under reduced pressure. Chloroform was removed under vacuum to obtain the product chitosan-g-(2,2,2-trifluoro-N-trifluoroacetyl-acetamide) (compound 1-3).

[0431] 1 H NMR (300MHz, CDCl3): ppm 1.06(m, 1H), 3.24 (m, 6H), 3.50(m, 2H), 3.56(m, 1H), 3.66 (m, 2H), 4.01(m, 1H), 4.30(m, 1H); 13 C NMR (300 MHz, CDCl3): 8.0, 26.1, 40.0, 52.0, 54.2, 63.6, 71.6, 75.6, 122.9, 168.6; 19 F NMR (CDCl3): ppm -77.4 (s)

[0432]

[0433] [Reaction Scheme 1-4] Synthesis of Chitosan-g-(C,C,C-trifluoro-N-trifluoromethanesulfonyl-methanesulfonylamide) (Compound 1-4)

[0434]

[0435] Triflic anhydride (10.0 g, 36 mmol) was added dropwise under a nitrogen atmosphere to a mixture of chitosan (34.2 g, 157.5 mmol) and triethylamine (4.0 g, 40 mmol) mixed in 40 ml of chloroform at -40°C. The solution was stirred at room temperature for 4 hours, and volatile substances were removed under reduced pressure. The remaining viscous liquid was dissolved in 30 ml of 4 M NaOH, washed three times with 25 ml of chloroform, and the aqueous component was neutralized with HCl, followed by washing three more times with 30 ml of chloroform. Subsequently, the organic extract was dried with anhydrous MgSO4 and filtered. Chloroform was removed under vacuum to obtain the product chitosan-g-(C,C,C-trifluoro-N-trifluoromethanesulfonyl-methanesulfonylamide) (Compound 1-4).

[0436] 1 H NMR (300MHz, CDCl3): ppm 2.08(m, 1H), 3.04(m, 1H), 3.17(m, 1H), 3.24 (m, 6H), 3.50(m, 2H), 3.66 (m, 2H), 3.91(m, 2H); 13 C NMR (300 MHz, CDCl3): 8.0, 26.1, 36.1, 52.0, 54.2, 69.1, 71.6, 71.7, 75.6, 146.1; 19 F NMR (CDCl3): ppm -77.8 (s)

[0437]

[0438] [Example 2]

[0439] [Reaction Scheme 2-1] Synthesis of Sulfuric Acid-Based Chitosan-g-(2,2,2-Trifluoroacetamide) Binder (Compound 2-1)

[0440]

[0441] Chitosan-g-(2,2,2-trifluoro-acetamide) (compound 1-1) (5.48 g, 17.5 mmol) was dissolved in an aqueous sulfuric acid solution (8.58 g, 8.75 mmol) at room temperature, then thoroughly washed with distilled water and stored again in distilled water to obtain the product sulfate-based chitosan-g-(2,2,2-trifluoro-acetamide) binder (compound 2-1).

[0442]

[0443] [Reaction Scheme 2-2] Synthesis of Sulfuric Acid-Based Chitosan-g-(C,C,C-Trifluoro-Methanesulfonamide) Binder (Compound 2-2)

[0444]

[0445] Chitosan-g-(C,C,C-trifluoro-methanesulfonamide) (Compound 1-2) (6.10 g, 17.5 mmol) was dissolved in an aqueous sulfuric acid solution (8.58 g, 8.75 mmol) at room temperature, then thoroughly washed with distilled water and stored again in distilled water to obtain the product sulfate-based chitosan-g-(C,C,C-trifluoro-methanesulfonamide) binder (Compound 2-2).

[0446]

[0447] [Reaction Scheme 2-3] Synthesis of Sulfuric Acid-Based Chitosan-g-(2,2,2-Trifluoro-N-Trifluoroacetyl-acetamide) Binder (Compound 2-3)

[0448]

[0449] Chitosan-g-(2,2,2-trifluoro-N-trifluoroacetyl-acetamide) (compound 1-3) (7.16 g, 17.5 mmol) was dissolved in an aqueous sulfuric acid solution (8.58 g, 8.75 mmol) at room temperature, then thoroughly washed with distilled water and stored again in distilled water to obtain the product sulfate-based chitosan-g-(2,2,2-trifluoro-N-trifluoroacetyl-acetamide) binder (compound 2-3).

[0450]

[0451] [Reaction Scheme 2-4] Synthesis of Sulfuric Acid-Based Chitosan-g-(C,C,C-Trifluoro-N-Trifluoromethanesulfonyl-methanesulfonylamide) Binder (Compound 1-4)

[0452]

[0453] Chitosan-g-(C,C,C-trifluoro-N-trifluoromethanesulfonyl-methanesulfonylamide) (Compound 1-4) (8.42 g, 17.5 mmol) was dissolved in an aqueous sulfuric acid solution (8.58 g, 8.75 mmol) at room temperature, then thoroughly washed with distilled water and stored again in distilled water to obtain the product sulfate-based chitosan-g-(C,C,C-trifluoro-N-trifluoromethanesulfonyl-methanesulfonylamide) binder (Compound 2-4).

[0454]

[0455] [Example 3]

[0456] [Reaction Scheme 3-1] Synthesis of Phosphate-based Chitosan-g-(2,2,2-trifluoroacetamide) Binder (Compound 3-1)

[0457]

[0458] Chitosan-g-(2,2,2-trifluoro-acetamide) (compound 1-1) (5.48 g, 17.5 mmol) was dissolved in an aqueous sodium phosphate solution (0.23 g, 0.238 mmol), thoroughly washed with distilled water, and stored again in distilled water to obtain the product phosphate-based chitosan-g-(2,2,2-trifluoro-acetamide) binder (compound 3-1).

[0459]

[0460] [Reaction Scheme 3-2] Synthesis of Phosphate-based Chitosan-g-(C,C,C-trifluoro-methanesulfonamide) Binder (Compound 3-2)

[0461]

[0462] Chitosan-g-(C,C,C-trifluoro-methanesulfonamide) (Compound 1-2) (6.10 g, 17.5 mmol) was dissolved in an aqueous sodium phosphate solution (0.23 g, 0.238 mmol) at room temperature, then thoroughly washed with distilled water and stored again in distilled water to obtain the product phosphate-based chitosan-g-(C,C,C-trifluoro-methanesulfonamide) binder (Compound 3-2).

[0463]

[0464] [Reaction Scheme 3-3] Synthesis of Phosphate-based Chitosan-g-(2,2,2-Trifluoro-N-Trifluoroacetyl-acetamide) Binder (Compound 3-3)

[0465]

[0466] Chitosan-g-(2,2,2-trifluoro-N-trifluoroacetyl-acetamide) (Compound 1-3) (7.16 g, 17.5 mmol) was dissolved in an aqueous sodium phosphate solution (0.23 g, 0.238 mmol) at room temperature, then thoroughly washed with distilled water and stored again in distilled water to obtain the product phosphate-based chitosan-g-(2,2,2-trifluoro-N-trifluoroacetyl-acetamide) binder (Compound 3-3).

[0467]

[0468] [Reaction Scheme 3-4] Synthesis of Phosphate-based Chitosan-g-(C,C,C-trifluoro-N-trifluoromethanesulfonyl-methanesulfonylamide) Binder (Compound 3-4)

[0469]

[0470] Chitosan-g-(C,C,C-trifluoro-N-trifluoromethanesulfonyl-methanesulfonylamide) (Compound 1-4) (8.42 g, 17.5 mmol) was dissolved in an aqueous sodium phosphate solution (0.23 g, 0.238 mmol) at room temperature, then thoroughly washed with distilled water and stored again in distilled water to obtain the product phosphate-based chitosan-g-(C,C,C-trifluoro-N-trifluoromethanesulfonyl-methanesulfonylamide) binder (Compound 3-4).

[0471]

[0472] [Example 4]

[0473] [Reaction Scheme 4-1] Synthesis of Tripolyphosphate-based Chitosan-g-(2,2,2-Trifluoro-acetamide) Binder (Compound 4-1)

[0474]

[0475] Chitosan-g-(2,2,2-trifluoro-acetamide) (compound 1-1) (5.48 g, 17.5 mmol) was dissolved in an aqueous solution of sodium tripolyphosphate (0.61 g, 0.238 mmol), thoroughly washed with distilled water, and stored again in distilled water to obtain the product tripolyphosphate-based chitosan-g-(2,2,2-trifluoro-acetamide) binder (compound 4-1).

[0476]

[0477] [Reaction Scheme 4-2] Synthesis of Tripolyphosphate-based Chitosan-g-(C,C,C-trifluoro-methanesulfonamide) Binder (Compound 4-2)

[0478]

[0479] Chitosan-g-(C,C,C-trifluoro-methanesulfonamide) (Compound 1-2) (6.10 g, 17.5 mmol) was dissolved in an aqueous solution of sodium tripolyphosphate (0.61 g, 0.238 mmol) at room temperature, then thoroughly washed with distilled water and stored again in distilled water to obtain the product tripolyphosphate-based chitosan-g-(C,C,C-trifluoro-methanesulfonamide) binder (Compound 4-2).

[0480]

[0481] [Reaction Scheme 4-3] Synthesis of Tripolyphosphate-based Chitosan-g-(2,2,2-Trifluoro-N-Trifluoroacetyl-acetamide) Binder (Compound 4-3)

[0482]

[0483] Chitosan-g-(2,2,2-trifluoro-N-trifluoroacetyl-acetamide) (Compound 1-3) (7.16 g, 17.5 mmol) was dissolved in an aqueous sodium tripolyphosphate solution (0.61 g, 0.238 mmol) at room temperature, then thoroughly washed with distilled water and stored again in distilled water to obtain the product tripolyphosphate-based chitosan-g-(2,2,2-trifluoro-N-trifluoroacetyl-acetamide) binder (Compound 4-3).

[0484]

[0485] [Reaction Scheme 4-4] Synthesis of Tripolyphosphate-based Chitosan-g-(C,C,C-Trifluoro-N-Trifluoromethanesulfonyl-methanesulfonylamide) Binder (Compound 4-4)

[0486]

[0487] [Example 5]

[0488] [Reaction Scheme 5-1] Synthesis of Citric Acid-Based Chitosan-g-(2,2,2-Trifluoroacetamide) Binder (Compound 5-1)

[0489]

[0490] An aqueous solution containing 1.1 wt% of chitosan-g-(2,2,2-trifluoro-acetamide) (Compound 1-1) and an aqueous solution containing 5 wt% of citric acid were prepared, respectively. 9.81 g of the above aqueous solution of chitosan-g-(2,2,2-trifluoro-acetamide) (Compound 1-1) and 0.24 g of the aqueous solution of citric acid were mixed and stirred at 1,500 rpm for 3 minutes, and then 150 o A citric acid-based chitosan-g-(2,2,2-trifluoroacetamide) binder (compound 6-1) was obtained by crosslinking at a temperature of C.

[0491]

[0492] [Reaction Scheme 5-2] Synthesis of Citric Acid-Based Chitosan-g-(C,C,C-Trifluoro-Methanesulfonamide) Binder (Compound 5-2)

[0493]

[0494] An aqueous solution containing 1.1 wt% of chitosan-g-(2,2,2-trifluoro-methanesulfonamide) (Compound 1-2) and an aqueous solution containing 5 wt% of citric acid were prepared, respectively. 9.81 g of the above aqueous solution of chitosan-g-(2,2,2-trifluoro-methanesulfonamide) (Compound 1-2) and 0.24 g of the aqueous solution of citric acid were mixed and stirred at 1,500 rpm for 3 minutes, and then 150 o A citric acid-based chitosan-g-(2,2,2-trifluoro-methanesulfonamide) binder (compound 5-2) was obtained by crosslinking at a temperature of C.

[0495]

[0496] [Reaction Scheme 5-3] Synthesis of citric acid-based chitosan-g-(2,2,2-trifluoro-N-trifluoroacetyl-acetamide) binder (Compound 5-3)

[0497]

[0498] An aqueous solution containing 1.1 wt% of chitosan-g-(2,2,2-trifluoro-N-trifluoroacetyl-acetamide) (Compound 1-3) and an aqueous solution containing 5 wt% of citric acid were prepared, respectively. 9.81 g of the above aqueous solution of chitosan-g-(2,2,2-trifluoro-N-trifluoroacetyl-acetamide) (Compound 1-3) and 0.24 g of the aqueous solution of citric acid were mixed and stirred at 1,500 rpm for 3 minutes, and then 150 o A citric acid-based chitosan-g-(2,2,2-trifluoro-N-trifluoroacetyl-acetamide) binder (compound 5-3) was obtained by crosslinking at a temperature of C.

[0499]

[0500] [Reaction Scheme 5-4] Synthesis of citric acid-based chitosan-g-(C,C,C-trifluoro-N-trifluoromethanesulfonyl-methanesulfonylamide) binder (Compound 5-4)

[0501]

[0502] An aqueous solution containing 1.1 wt% of chitosan-g-(C,C,C-trifluoro-N-trifluoromethanesulfonyl-methanesulfonylamide) (Compound 1-4) and an aqueous solution containing 5 wt% of citric acid were prepared, respectively. 9.81 g of the aqueous solution of chitosan-g-(C,C,C-trifluoro-N-trifluoromethanesulfonyl-methanesulfonylamide) (Compound 1-4) and 0.24 g of the aqueous solution of citric acid were mixed and stirred at 1,500 rpm for 3 minutes, and then 150 o A citric acid-based chitosan-g-(C,C,C-trifluoro-N-trifluoromethanesulfonyl-methanesulfonylamide) binder (compound 5-4) was obtained by crosslinking at a temperature of C.

[0503]

[0504] [Example 6]

[0505] [Reaction Scheme 6-1] Synthesis of glutaraldehyde-based chitosan-g-(2,2,2-trifluoroacetamide) binder (Compound 6-1)

[0506]

[0507] 80 μl of 25% glutaraldehyde was added dropwise to 50 ml of a solution in which 2% concentration of chitosan-g-(2,2,2-trifluoro-acetamide) (Compound 1-1) was dissolved in a 1% concentration aqueous acetic acid solution while stirring vigorously for 1 hour. Then, 7 ml of the solution was poured into a polystyrene dish and dried at room temperature until it could be peeled off to obtain a glutaraldehyde-based chitosan-g-(2,2,2-trifluoro-acetamide) binder (Compound 6-1).

[0508]

[0509] [Reaction Scheme 6-2] Synthesis of glutaraldehyde-based chitosan-g-(C,C,C-trifluoro-methanesulfonamide) binder (Compound 6-2)

[0510]

[0511] 80 μl of 25% glutaraldehyde was added dropwise to 50 ml of a solution in which 2% concentration of chitosan-g-(C,C,C-trifluoro-methanesulfonamide) (Compound 1-2) was dissolved in a 1% concentration aqueous acetic acid solution while stirring vigorously for 1 hour. Then, 7 ml of the solution was poured into a polystyrene dish and dried at room temperature until it could be peeled off to obtain a glutaraldehyde-based chitosan-g-(C,C,C-trifluoro-methanesulfonamide) binder (Compound 6-2).

[0512]

[0513] [Reaction Scheme 6-3] Synthesis of glutaraldehyde-based chitosan-g-(2,2,2-trifluoro-N-trifluoroacetyl-acetamide) binder (Compound 6-3)

[0514]

[0515] 80 μl of 25% glutaraldehyde was added dropwise to 50 ml of a solution in which 2% concentration of chitosan-g-(2,2,2-trifluoro-N-trifluoroacetyl-acetamide) (Compound 1-3) was dissolved in a 1% concentration aqueous acetic acid solution while vigorously stirring for 1 hour. Then, 7 ml of the solution was poured into a polystyrene dish and dried at room temperature until it could be peeled off to obtain a glutaraldehyde-based chitosan-g-(2,2,2-trifluoro-N-trifluoroacetyl-acetamide) binder (Compound 6-3).

[0516]

[0517] [Reaction Scheme 6-4] Synthesis of glutaraldehyde-based chitosan-g-(C,C,C-trifluoro-N-trifluoromethanesulfonyl-methanesulfonylamide) binder (Compound 6-4)

[0518]

[0519] 80 μl of 25% glutaraldehyde was added dropwise to 50 ml of a solution in which 2% concentration of chitosan-g-(C,C,C-trifluoro-N-trifluoromethanesulfonyl-methanesulfonylamide) (Compound 1-4) was dissolved in a 1% concentration aqueous acetic acid solution while vigorously stirring for 1 hour. Then, 7 ml of the solution was poured into a polystyrene dish and dried at room temperature until it could be peeled off to obtain a glutaraldehyde-based chitosan-g-(C,C,C-trifluoro-N-trifluoromethanesulfonyl-methanesulfonylamide) binder (Compound 6-4).

[0520]

[0521] [Example 7]

[0522] [Reaction Scheme 7-1] Synthesis of Polyaniline-based Chitosan-g-(2,2,2-Trifluoro-acetamide) Binder (Compound 7-1)

[0523]

[0524] A chitosan-g-(2,2,2-trifluoroacetamide) (Compound 1-1) solution was prepared by dissolving 2.0 g of chitosan-g-(2,2,2-trifluoroacetamide) (Compound 1-1) in 200 ml of 1 mol HCl solution. A chitosan-g-(2,2,2-trifluoroacetamide)-polyaniline solution was prepared by adding 0.98 ml of aniline monomer dropwise to the chitosan-g-(2,2,2-trifluoroacetamide) (Compound 1-1) solution at room temperature. After completely dissolving the aniline, a 1 mol HCl solution was added dropwise to the chitosan-polyaniline solution to achieve a 1:1 molar ratio with the aniline monomer. Ammonium persulfate was used as an initiator for graft polymerization. The mixture was stirred for 24 hours under a nitrogen atmosphere. The reaction mixture was neutralized with 5 mol of NaOH solution, and the graft-polymerized polymer was precipitated with an excess of ethanol. The resulting precipitate was washed with N-methylpyrrolidinone to remove the homopolymer polyaniline from the copolymer, then washed with acetone and dried under vacuum at 40 °C to obtain a polyaniline-based chitosan-g-(2,2,2-trifluoroacetamide) binder (Compound 7-1).

[0525]

[0526] [Reaction Scheme 7-2] Synthesis of Polyaniline-based Chitosan-g-(C,C,C-trifluoro-methanesulfonamide) Binder (Compound 7-2)

[0527]

[0528] A chitosan-g-(C,C,C-trifluoro-methanesulfonamide) (Compound 1-2) solution was prepared by dissolving 2.0 g of chitosan-g-(C,C,C-trifluoro-methanesulfonamide) (Compound 1-2) in 200 ml of 1 M HCl solution. A chitosan-g-(C,C,C-trifluoro-methanesulfonamide)-polyaniline solution was prepared by adding 0.98 ml of aniline monomer dropwise to the chitosan-g-(C,C,C-trifluoro-methanesulfonamide) (Compound 1-2) solution at room temperature. After completely dissolving the aniline, a 1 mol HCl solution was added dropwise to the chitosan-g-(C,C,C-trifluoro-methanesulfonamide)-polyaniline solution in a 1:1 molar ratio with the aniline monomer. Ammonium persulfate was used as an initiator for graft polymerization. The mixture was stirred for 24 hours under a nitrogen atmosphere. After the reaction was complete, the mixture was neutralized with 5 mol of NaOH solution, and the graft-polymerized polymer was precipitated with an excess of ethanol. The resulting precipitate was washed with N-methylpyrrolidinone to remove the homopolymer polyaniline from the copolymer, then washed with acetone and dried under vacuum at 40 °C to obtain a polyaniline-based chitosan-g-(C,C,C-trifluoro-methanesulfonamide) binder (Compound 7-2).

[0529]

[0530] [Reaction Scheme 7-3] Synthesis of Polyaniline-based Chitosan-g-(2,2,2-Trifluoro-N-Trifluoroacetyl-acetamide) Binder (Compound 7-3)

[0531]

[0532] A chitosan-g-(2,2,2-trifluoro-N-trifluoroacetyl-acetamide) (compound 1-3) solution was prepared by dissolving 2.0 g of chitosan-g-(2,2,2-trifluoro-N-trifluoroacetyl-acetamide) (compound 1-3) in 200 mL of 1 mol HCl solution. A chitosan-g-(2,2,2-trifluoro-N-trifluoroacetyl-acetamide)-polyaniline solution was prepared by adding 0.98 ml of aniline monomer dropwise to the chitosan-g-(2,2,2-trifluoro-N-trifluoroacetyl-acetamide) (compound 1-3) solution at room temperature. After completely dissolving the aniline, 1 mol HCl solution was added dropwise to the chitosan-g-(2,2,2-trifluoro-N-trifluoroacetyl-acetamide)-polyaniline solution in a 1:1 molar ratio with the aniline monomer. Ammonium persulfate was used as an initiator for graft polymerization. The mixture was stirred for 24 hours under a nitrogen atmosphere. After the reaction was complete, the mixture was neutralized with 5 mol NaOH solution, and the graft-polymerized polymer was precipitated with an excess amount of ethanol. The resulting precipitate was washed with N-methylpyrrolidinone to remove the homopolymer polyaniline from the copolymer, then washed with acetone and dried under vacuum at 40 °C to obtain a polyaniline-based chitosan-g-(2,2,2-trifluoro-N-trifluoroacetyl-acetamide) binder (Compound 7-3).

[0533]

[0534] [Reaction Scheme 7-4] Synthesis of Polyaniline-based Chitosan-g-(C,C,C-Trifluoro-N-Trifluoromethanesulfonyl-methanesulfonylamide) Binder (Compound 7-4)

[0535]

[0536] A solution of chitosan-g-(C,C,C-trifluoro-N-trifluoromethanesulfonyl-methanesulfonylamide) (Compound 1-4) was prepared by dissolving 2.0 g of chitosan-g-(C,C,C-trifluoro-N-trifluoromethanesulfonyl-methanesulfonylamide) (Compound 1-4) in 200 ml of 1 mol HCl solution. A solution of chitosan-g-(C,C,C-trifluoro-N-trifluoromethanesulfonyl-methanesulfonylamide)-polyaniline was prepared by adding 0.98 ml of aniline monomer dropwise to the chitosan-g-(C,C,C-trifluoro-N-trifluoromethanesulfonyl-methanesulfonylamide) (Compound 1-4) solution at room temperature. After completely dissolving the aniline, 1 mol HCl solution was added dropwise to the chitosan-g-(2,2,2-trifluoro-N-trifluoroacetyl-acetamide)-polyaniline solution in a 1:1 molar ratio with the aniline monomer. Ammonium persulfate was used as an initiator for graft polymerization. The mixture was stirred for 24 hours under a nitrogen atmosphere. After the reaction was complete, the mixture was neutralized with 5 mol NaOH solution, and the graft-polymerized polymer was precipitated with an excess amount of ethanol. The resulting precipitate was washed with N-methylpyrrolidinone to remove the homopolymer polyaniline from the copolymer, then washed with acetone and dried under vacuum at 40 °C to obtain a polyaniline-based chitosan-g-(C,C,C-trifluoro-N-trifluoromethanesulfonyl-methanesulfonylamide) binder (Compound 7-4).

[0537]

[0538] [Reaction Scheme 7-5] Synthesis of Poly(Aniline-2,2,2-Trifluoro-N-Phenyl-Acetamide)-based Chitosan-g-(2,2,2-Trifluoro-Acetamide) Binder (Compound 7-5)

[0539]

[0540] A chitosan-g-(2,2,2-trifluoro-acetamide) (Compound 1-1) solution was prepared by dissolving 2.0 g of chitosan-g-(2,2,2-trifluoro-acetamide) (Compound 1-1) in 200 ml of 1 mol HCl solution. A chitosan-g-(2,2,2-trifluoro-acetamide)-polyaniline solution was prepared by adding 0.49 ml of aniline monomer dropwise to the chitosan-g-(2,2,2-trifluoro-acetamide) (Compound 1-1) solution at room temperature. After completely dissolving the aniline, a 1 mol HCl solution was added dropwise to the chitosan-polyaniline solution such that the aniline and 2,2,2-trifluoro-N-phenyl-acetamide monomers were added in a 1:1 molar ratio. Ammonium persulfate was used as an initiator for graft polymerization. The mixture was stirred for 24 hours under a nitrogen atmosphere. After the reaction was complete, the mixture was neutralized with 5 mol of NaOH solution, and the graft-polymerized polymer was precipitated with an excess of ethanol. The resulting precipitate was washed with N-methylpyrrolidinone to remove the homopolymers polyaniline and poly(2,2,2-trifluoro-N-phenyl-acetamide) from the copolymer, then washed with acetone and dried under vacuum at 40 °C to obtain a poly(aniline-2,2,2-trifluoro-N-phenyl-acetamide)-based chitosan-g-(2,2,2-trifluoro-acetamide) binder (Compound 7-5).

[0541]

[0542] [Reaction Scheme 7-6] Synthesis of Poly(Aniline-C,C,C-Trifluoro-N-Phenyl-Methanesulfonamide)-based Chitosan-g-(C,C,C-Trifluoro-Methanesulfonamide) Binder (Compound 7-6)

[0543]

[0544] A chitosan-g-(C,C,C-trifluoro-methanesulfonamide) (Compound 1-2) solution was prepared by dissolving 2.0 g of chitosan-g-(C,C,C-trifluoro-methanesulfonamide) (Compound 1-2) in 200 ml of 1 mol HCl solution. A chitosan-g-(C,C,C-trifluoro-methanesulfonamide)-polyaniline solution was prepared by adding 0.49 ml of aniline monomer dropwise to the chitosan-g-(C,C,C-trifluoro-methanesulfonamide) (Compound 1-2) solution at room temperature. After completely dissolving the aniline, a 1 mol HCl solution was added dropwise to the chitosan-polyaniline solution such that the aniline and 2,2,2-trifluoro-N-phenyl-acetamide monomers were added in a 1:1 molar ratio. Ammonium persulfate was used as an initiator for graft polymerization. The mixture was stirred for 24 hours under a nitrogen atmosphere. After the reaction was complete, the mixture was neutralized with 5 mol of NaOH solution, and the graft-polymerized polymer was precipitated with an excess of ethanol. The resulting precipitate was washed with N-methylpyrrolidinone to remove the homopolymers polyaniline and poly(2,2,2-trifluoro-N-phenyl-methanesulfonamide) from the copolymer, then washed with acetone and dried under vacuum at 40 °C to obtain a poly(aniline-2-trifluoromethanesulfonylamino-benzoic acid)-based chitosan-g-(C,C,C-trifluoro-methanesulfonamide) binder (Compound 7-6).

[0545]

[0546] [Reaction Scheme 7-7] Synthesis of Poly(aniline-2,2,2-trifluoro-N-phenyl-acetamide)-based Chitosan-g-(2,2,2-trifluoro-N-trifluoroacetyl-acetamide) Binder (Compound 7-7)

[0547]

[0548] A chitosan-g-(2,2,2-trifluoro-N-trifluoroacetyl-acetamide) (compound 1-3) solution was prepared by dissolving 2.0 g of chitosan-g-(2,2,2-trifluoro-N-trifluoroacetyl-acetamide) (compound 1-3) in 200 ml of 1 mol HCl solution. A chitosan-g-(2,2,2-trifluoro-N-trifluoroacetyl-acetamide)-polyaniline solution was prepared by adding 0.49 ml of aniline monomer dropwise to the chitosan-g-(2,2,2-trifluoro-N-trifluoroacetyl-acetamide) (compound 1-3) solution at room temperature. After completely dissolving the aniline, 1 mol HCl solution was added dropwise to the chitosan-polyaniline solution such that the aniline and 2,2,2-trifluoro-N-phenyl-acetamide monomers were in a 1:1 molar ratio. Ammonium persulfate was used as an initiator for graft polymerization. The mixture was stirred for 24 hours under a nitrogen atmosphere. After the reaction was complete, the mixture was neutralized with 5 mol NaOH solution, and the graft-polymerized polymer was precipitated with an excess amount of ethanol. The generated precipitate was washed with N-methylpyrrolidinone to remove the homopolymer polyaniline and poly(2,2,2-trifluoro-N-phenyl-acetamide) from the copolymer, then washed with acetone and dried under vacuum at 40°C to obtain a poly(aniline-2,2,2-trifluoro-N-phenyl-acetamide)-based chitosan-g-(2,2,2-trifluoro-N-trifluoroacetyl-acetamide) binder (compound 7-7).

[0549]

[0550] [Reaction Scheme 7-8] Synthesis of Poly(Aniline-C,C,C-Trifluoro-N-Phenyl-Methanesulfonamide)-based Chitosan-g-(C,C,C-Trifluoro-N-Trifluoromethanesulfonyl-Methanesulfonylamide) Binder (Compound 7-8)

[0551]

[0552] 2.0 g of chitosan-g-(C,C,C-trifluoro-N-trifluoromethanesulfonyl-methanesulfonylamide) (Compound 1-4) in 100 ml of 1 mol HCl solution 90 o A solution of chitosan-g-(C,C,C-trifluoro-N-trifluoromethanesulfonyl-methanesulfonilamide) (Compound 1-4) was prepared by dissolving at C. At room temperature, 0.49 ml of aniline monomer was added dropwise to the chitosan-g-(C,C,C-trifluoro-N-trifluoromethanesulfonyl-methanesulfonilamide) (Compound 1-4) solution. After 0.5 hours, the solution was 5 o After cooling to C, an initiator solution prepared by mixing 0.613 g of ammonium persulfate with 10 ml of 1 mol HCl solution was added dropwise to the chitosan-aniline-C,C,C-trifluoro-N-phenyl-methanesulfonamide solution such that the molar ratio of aniline-anthranilate monomer to ammonium persulfate was 1:1. The mixture was stirred for 24 hours under a nitrogen atmosphere, and a dark green product was obtained. After the reaction was complete, the mixture was neutralized with 5 mol NaOH solution, and the copolymer was precipitated with a 1:1 amount of ethanol. The unpolymerized polyaniline homopolymer present in the precipitate was removed by washing with N-methylpyrrolidinone, then washed with acetone and dried under vacuum at 40°C to obtain a poly(aniline-C,C,C-trifluoro-N-phenyl-methanesulfonamide)-based chitosan-g-(C,C,C-trifluoro-N-trifluoromethanesulfonyl-methanesulfonylamide) binder (compound 7-8).

[0553]

[0554] [Reaction Scheme 7-9] Synthesis of Poly(aniline-anthranilic acid)-based Chitosan-g-(2,2,2-trifluoroacetamide) Binder (Compound 7-9)

[0555]

[0556] 1.0 g of chitosan-g-(2,2,2-trifluoroacetamide) (Compound 1-1) in 100 ml of 1 mol HCl solution 90o A chitosan-g-(2,2,2-trifluoro-acetamide) (Compound 1-1) solution was prepared by dissolving at C. At room temperature, 0.125 g of aniline monomer and 0.184 g of anthranilic acid monomer were added dropwise to the chitosan-(2,2,2-trifluoro-acetamide) (Compound 1-1) solution. After 0.5 hours, the solution was 5 o After cooling to °C, an initiator solution prepared by mixing 0.613 g of ammonium persulfate with 10 ml of 1 mol HCl solution was added dropwise to the chitosan-aniline-anthranilic acid solution such that the molar ratio of aniline-anthranilic acid monomer to ammonium persulfate was 1:1. The mixture was stirred for 24 hours under a nitrogen atmosphere, and a dark green product was obtained. After the reaction was complete, the mixture was neutralized with 5 mol NaOH solution, and the copolymer was precipitated with an excess amount of ethanol. The unpolymerized polyaniline homopolymer present in the precipitate was removed by washing with N-methylpyrrolidinone, followed by washing with acetone and drying under vacuum at 40 °C to obtain a poly(aniline-anthranilic acid)-based chitosan-g-(2,2,2-trifluoroacetamide) binder (Compound 7-9).

[0557]

[0558] [Reaction Scheme 7-10] Synthesis of Poly(aniline-anthranilate)-based Chitosan-g-(2,2,2-trifluoro-methanesulfonamide) Binder (Compound 7-10)

[0559]

[0560] 1.0 g of chitosan-g-(2,2,2-trifluoro-methanesulfonamide) (Compound 1-2) in 100 ml of 1 mol HCl solution 90 oA chitosan-g-(2,2,2-trifluoro-methanesulfonamide) (Compound 1-2) solution was prepared by dissolving at C. At room temperature, 0.125 g of aniline monomer and 0.184 g of anthranilic acid monomer were added dropwise to the chitosan-(2,2,2-trifluoro-methanesulfonamide) (Compound 1-2) solution. After 0.5 hours, the solution was 5 o After cooling to °C, an initiator solution prepared by mixing 0.613 g of ammonium persulfate with 10 ml of 1 mol HCl solution was added dropwise to the chitosan-aniline-anthranilic acid solution such that the molar ratio of aniline-anthranilic acid monomer to ammonium persulfate was 1:1. The mixture was stirred for 24 hours under a nitrogen atmosphere, and a dark green product was obtained. After the reaction was complete, the mixture was neutralized with 5 mol NaOH solution, and the copolymer was precipitated with an excess amount of ethanol. The unpolymerized polyaniline homopolymer present in the precipitate was removed by washing with N-methylpyrrolidinone, followed by washing with acetone and drying under vacuum at 40 °C to obtain a poly(aniline-anthranilic acid)-based chitosan-g-(2,2,2-trifluoro-methanesulfonamide) binder (Compound 7-10).

[0561]

[0562] [Reaction Scheme 7-11] Synthesis of Poly(aniline-anthranilic acid)-based Chitosan-g-(2,2,2-trifluoro-N-trifluoroacetyl-acetamide) Binder (Compound 7-11)

[0563]

[0564] 1.0 g of chitosan-g-(2,2,2-trifluoro-N-trifluoroacetyl-acetamide) (Compound 1-3) in 100 ml of 1 mol HCl solution 90 oA chitosan-g-(2,2,2-trifluoro-N-trifluoroacetyl-acetamide) (Compound 1-3) solution was prepared by dissolving at C. At room temperature, 0.125 g of aniline monomer and 0.184 g of anthranilic acid monomer were added dropwise to the chitosan-(2,2,2-trifluoro-N-trifluoroacetyl-acetamide) (Compound 1-3) solution. After 0.5 hours, the solution was 5 o After cooling to °C, an initiator solution prepared by mixing 0.613 g of ammonium persulfate with 10 ml of 1 mol HCl solution was added dropwise to the chitosan-aniline-anthranilic acid solution such that the molar ratio of aniline-anthranilic acid monomer to ammonium persulfate was 1:1. The mixture was stirred for 24 hours under a nitrogen atmosphere, and a dark green product was obtained. After the reaction was complete, the mixture was neutralized with 5 mol NaOH solution, and the copolymer was precipitated with an excess amount of ethanol. The unpolymerized polyaniline homopolymer present in the precipitate was removed by washing with N-methylpyrrolidinone, followed by washing with acetone and drying under vacuum at 40 °C to obtain a poly(aniline-anthranilic acid)-based chitosan-g-(2,2,2-trifluoro-N-trifluoroacetyl-acetamide) binder (Compound 7-11).

[0565]

[0566] [Reaction Scheme 7-12] Synthesis of Poly(aniline-anthranilic acid)-based Chitosan-g-(C,C,C-trifluoro-N-trifluoromethanesulfonyl-methanesulfonylamide) Binder (Compound 7-12)

[0567]

[0568] 1.0 g of chitosan-g-(C,C,C-trifluoro-N-trifluoromethanesulfonyl-methanesulfonylamide) (Compound 1-4) in 100 ml of 1 mol HCl solution 90 oA solution of chitosan-g-(C,C,C-trifluoro-N-trifluoromethanesulfonyl-methanesulfonilamide) (Compound 1-4) was prepared by dissolving at C. At room temperature, 0.125 g of aniline monomer and 0.184 g of anthranilic acid monomer were added drop by drop to the chitosan-g-(C,C,C-trifluoro-N-trifluoromethanesulfonyl-methanesulfonilamide) (Compound 1-4) solution. After 0.5 hours, the solution was 5 o After cooling to C, an initiator solution prepared by mixing 0.613 g of ammonium persulfate with 10 ml of 1 mol HCl solution was added dropwise to the chitosan-aniline-anthranilic acid solution such that the molar ratio of aniline-anthranilic acid monomer to ammonium persulfate was 1:1. The mixture was stirred for 24 hours under a nitrogen atmosphere, and a dark green product was obtained. After the reaction was complete, the mixture was neutralized with 5 mol NaOH solution, and the copolymer was precipitated with a 1:1 amount of ethanol. The unpolymerized polyaniline homopolymer present in the precipitate was removed by washing with N-methylpyrrolidinone, then washed with acetone and dried under vacuum at 40°C to obtain a poly(aniline-anthranilic acid)-based chitosan-g-(C,C,C-trifluoro-N-trifluoromethanesulfonyl-methanesulfonylamide) binder (compound 7-12).

[0569]

[0570] [Reaction Scheme 7-13] Synthesis of Poly(aniline-2-(2,2,2-trifluoro-acetylamino)-benzoic acid)-based Chitosan-g-(2,2,2-trifluoro-acetamide) Binder (Compound 7-13)

[0571]

[0572] 1.0 g of chitosan-g-(2,2,2-trifluoroacetamide) (Compound 1-1) in 100 ml of 1 mol HCl solution 90 oA chitosan-g-(2,2,2-trifluoro-acetamide) (Compound 1-1) solution was prepared by dissolving at C. At room temperature, 0.125 g of aniline monomer and 0.184 g of 2-(2,2,2-trifluoro-acetylamino)-benzoic acid monomer were added dropwise to the chitosan-(2,2,2-trifluoro-acetamide) (Compound 1-1) solution. After 0.5 hours, the solution was 5 o After cooling to C, an initiator solution prepared by mixing 0.613 g of ammonium persulfate with 10 ml of 1 mol HCl solution was added dropwise to the chitosan-aniline-2-(2,2,2-trifluoro-acetylamino)-benzoic acid solution such that the molar ratio of aniline-anthranilic acid monomer to ammonium persulfate was 1:1. The mixture was stirred for 24 hours under a nitrogen atmosphere, and a dark green product was obtained. After the reaction was complete, the mixture was neutralized with 5 mol NaOH solution, and the copolymer was precipitated with a 1:1 amount of ethanol. The unpolymerized polyaniline homopolymer present in the precipitate was removed by washing with N-methylpyrrolidinone, then washed with acetone and dried under vacuum at 40°C to obtain a poly(aniline-2-(2,2,2-trifluoro-acetylamino)-benzoic acid)-based chitosan-g-(2,2,2-trifluoro-acetamide) binder (compound 7-13).

[0573]

[0574] [Reaction Scheme 7-14] Synthesis of Poly(aniline-2-trifluoromethanesulfonylamino-benzoic acid)-based Chitosan-g-(2,2,2-trifluoromethanesulfonamide) Binder (Compound 7-14)

[0575]

[0576] 1.0 g of chitosan-g-(2,2,2-trifluoro-methanesulfonamide) (Compound 1-2) in 100 ml of 1 mol HCl solution 90 oA chitosan-g-(2,2,2-trifluoro-methanesulfonamide) (Compound 1-2) solution was prepared by dissolving at C. At room temperature, 0.125 g of aniline monomer and 0.184 g of 2-trifluoromethanesulfonylamino-benzoic acid monomer were added dropwise to the chitosan-(2,2,2-trifluoro-methanesulfonamide) (Compound 1-2) solution. After 0.5 hours, the solution was 5 o After cooling to C, an initiator solution prepared by mixing 0.613 g of ammonium persulfate with 10 ml of 1 mol HCl solution was added dropwise to the chitosan-aniline-2-trifluoromethanesulfonylamino-benzoic acid solution such that the molar ratio of aniline-anthranilic acid monomer to ammonium persulfate was 1:1. The mixture was stirred for 24 hours under a nitrogen atmosphere, and a dark green product was obtained. After the reaction was complete, the mixture was neutralized with 5 mol NaOH solution, and the copolymer was precipitated with a 1:1 amount of ethanol. The unpolymerized polyaniline homopolymer present in the precipitate was removed by washing with N-methylpyrrolidinone, then washed with acetone and dried under vacuum at 40°C to obtain a poly(aniline-2-trifluoromethanesulfonylamino-benzoic acid)-based chitosan-g-(2,2,2-trifluoro-methanesulfonamide) binder (compound 7-14).

[0577]

[0578] [Reaction Scheme 7-15] Synthesis of Poly(aniline-2-(2,2,2-trifluoro-acetylamino)-benzoic acid)-based Chitosan-g-(2,2,2-trifluoro-N-trifluoroacetyl-acetamide) Binder (Compound 7-15)

[0579]

[0580] 1.0 g of chitosan-g-(2,2,2-trifluoro-N-trifluoroacetyl-acetamide) (Compound 1-3) in 100 ml of 1 mol HCl solution 90 oA chitosan-g-(2,2,2-trifluoro-N-trifluoroacetyl-acetamide) (Compound 1-3) solution was prepared by dissolving at C. At room temperature, 0.125 g of aniline monomer and 0.184 g of 2-(2,2,2-trifluoro-acetylamino)-benzoic acid monomer were added dropwise to the chitosan-(2,2,2-trifluoro-N-trifluoroacetyl-acetamide) (Compound 1-3) solution. After 0.5 hours, the solution was 5 o After cooling to C, an initiator solution prepared by mixing 0.613 g of ammonium persulfate with 10 ml of 1 mol HCl solution was added dropwise to the chitosan-aniline-2-(2,2,2-trifluoro-acetylamino)-benzoic acid solution such that the molar ratio of aniline-2-(2,2,2-trifluoro-acetylamino)-benzoic acid monomer to ammonium persulfate was 1:1. The mixture was stirred for 24 hours under a nitrogen atmosphere, and a dark green product was obtained. After the reaction was complete, the mixture was neutralized with 5 mol NaOH solution, and the copolymer was precipitated with a 1:1 amount of ethanol. The unpolymerized polyaniline homopolymer present in the precipitate was removed by washing with N-methylpyrrolidinone, then washed with acetone and dried under vacuum at 40°C to obtain a poly(aniline-2-(2,2,2-trifluoro-acetylamino)-benzoic acid)-based chitosan-g-(2,2,2-trifluoro-N-trifluoroacetyl-acetamide) binder (compound 7-15).

[0581]

[0582] [Reaction Scheme 7-16] Synthesis of Poly(aniline-2-trifluoromethanesulfonylamino-benzoic acid)-based Chitosan-g-(C,C,C-trifluoro-N-trifluoromethanesulfonyl-methanesulfonylamide) Binder (Compound 7-16)

[0583]

[0584] 1.0 g of chitosan-g-(C,C,C-trifluoro-N-trifluoromethanesulfonyl-methanesulfonylamide) (Compound 1-4) in 100 ml of 1 mol HCl solution 90 o A solution of chitosan-g-(C,C,C-trifluoro-N-trifluoromethanesulfonyl-methanesulfonilamide) (Compound 1-4) was prepared by dissolving at C. At room temperature, 0.125 g of aniline monomer and 0.184 g of 2-trifluoromethanesulfonylamino-benzoic acid monomer were added dropwise to the chitosan-g-(C,C,C-trifluoro-N-trifluoromethanesulfonyl-methanesulfonilamide) (Compound 1-4) solution. After 0.5 hours, the solution was 5 o After cooling to C, an initiator solution prepared by mixing 0.613 g of ammonium persulfate with 10 ml of 1 mol HCl solution was added dropwise to the chitosan-aniline-2-trifluoromethanesulfonylamino-benzoic acid solution such that the molar ratio of aniline-2-trifluoromethanesulfonylamino-benzoic acid monomer to ammonium persulfate was 1:1. The mixture was stirred for 24 hours under a nitrogen atmosphere, and a dark green product was obtained. After the reaction was complete, the mixture was neutralized with 5 mol NaOH solution, and the copolymer was precipitated with a 1:1 amount of ethanol. The unpolymerized polyaniline homopolymer present in the precipitate was removed by washing with N-methylpyrrolidinone, then washed with acetone and dried under vacuum at 40°C to obtain a poly(aniline-2-trifluoromethanesulfonylamino-benzoic acid)-based chitosan-g-(C,C,C-trifluoro-N-trifluoromethanesulfonyl-methanesulfonylamide) binder (compound 7-16).

[0585]

[0586] [Experimental Example 1]

[0587] In this study, different active materials, conductive agents, binders, and conductive polymers were used.

[0588] Silicon was selected as the anode active material because it has the highest theoretical discharge capacity of 4200 mAh / g among alloy anode materials. Carbon Super P was used as the primary C-conducting agent because it is one of the most commonly used C-conducting agents. CNF was used as the C-conducting agent because it has a much higher conductivity than Carbon Super P. Chitosan was tested as a binder because it is one of the cheapest and most abundant biopolymers found in nature and has also been shown to improve the cycling performance of the electrode compared to PVDF. Chitosan TPP, an ionic cross-linked polymer of chitosan cross-linked with sodium tripolyphosphate, was used as a second binder to investigate its suitability for the Si anode because it was found to form a much stronger gel than chitosan due to its cross-linked structure, which can enhance the binding effect of chitosan by maintaining Si and C nanoparticles densely within the cross-linked binder structure.

[0589] To compare the experimental results using chitosan and chitosan TPP as new binders, the most commonly used commercial binder PVDF and two well-researched biopolymer binders, carboxymethyl cellulose and sodium alginate, were used as benchmarks.

[0590] In relation to battery manufacturing and testing, electrochemical tests were performed on pouch cells to verify cycling performance, rate capability, charge-discharge profiles, and internal resistance characteristics. Different material characterization techniques were adopted to understand the morphology and chemical structure of different components present in the anode or cathode complex.

[0591]

[0592] [Experimental Example 2] Material

[0593] Silicon nanoparticles (<100 nm, 98%, CAS No.: 7440-21-3) were sourced from Aldrich. NCM811 was sourced from Welcos as the cathode material. Chitosan (medium molecular weight, CAS No.: 9012-76-4), sodium alginate (medium viscosity, CAS No.: 9005-38-3), and sodium carboxymethyl cellulose (Mw-600,000, CAS No.: 9002-32-4) were sourced from Aldrich. PVDF (<99.5%, Mw-600,000) was obtained from MTI Corporation. Acetic acid and N-methyl-2-pyrrolidone (NMP) were used as solvents for chitosan and PVDF, respectively, and were obtained from Aldrich.

[0594] The electrolyte used was prepared by dissolving 1M LiPF6 in ethylene carbonate / dimethyl carbonate (1:1, v / v) purchased from Dodochem. Carbon Super P and carbon nanofibers were obtained from Aldrich and used as received.

[0595]

[0596] [Example 8] Preparation of Binder Gel Solution

[0597] The suitability of chitosan as an active material for Si anode binders was investigated using chitosan as the primary biopolymer. PVDF and alginate were used as Si anode binders to compare with the performance of chitosan. Additionally, CMC was used as a Si anode binder for comparison purposes. Approximately 2% binder solutions were prepared in beakers while stirring with a magnetic stirrer, and the preparation conditions are listed in Table 1. Chitosan solutions ranging from 1% m / v to 5% m / v were prepared in 1% v / v acetic acid in water. The 1% solution was thin, while the 3% to 5% chitosan solutions were very viscous, requiring a long time for mixing. Anode slurries were prepared using chitosan solutions of different concentrations and cast onto copper foil.

[0598] It was found that a slurry prepared with 2% chitosan had the desired concentration for casting on copper foil. Additionally, the high-concentration binder did not mix properly with Si and C during ball milling, resulting in a non-uniform slurry. PVDF solutions are mainly used at a 2% m / v concentration in NMP, while sodium alginate and CMC were previously used as 2% m / v aqueous solutions for Si anodes.

[0599] Ionic crosslinked hybrid binders were prepared by mixing alginate and chitosan binder gels with their respective crosslinking agents, calcium and sodium tripolyphosphate. 14 ml of a 6 mg / mL aqueous sodium tripolyphosphate (TPP) solution was added dropwise to 35 ml of a 2% chitosan aqueous solution with 1% (v / v) acetic acid under mechanical stirring at 300 rpm for 48 hours. Low concentrations of TPP resulted in a gel solution with low viscosity due to a low degree of crosslinking. Viscosity and the degree of crosslinking increased with increasing TPP concentration. Low viscosity and low degree of crosslinking result in low binder strength, while excessive viscosity and excessive degree of crosslinking result in a binder gel that cannot be used to make an anode slurry due to significant particle aggregation during mixing in a ball mill. A 6 mg / mL TPP solution is combined with 35 mL of a 2% chitosan aqueous solution containing 1% (v / v) acetic acid to form an optimal binder gel with a relatively high degree of crosslinking and perfect viscosity, which helps to form a strong but uniform anode slurry.

[0600] The alginate-calcium crosslinking binder is Ca2 to the alginate gel. + It was similarly prepared by adding ions (obtained by dissolving calcium chloride in deionized water) and mechanically stirring at 300 rpm for 24 hours while maintaining a molar ratio of 0.15.

[0601]

[0602] [Comparative Example 1] Preparation of electrode composite slurry

[0603] The anode slurry was prepared by mixing the active material Si nanoparticles, the conductor Super P or CNF, and a binder gel solution in a ball mill operated at 400 rpm for 6 hours. The ratios of the active material, conductor, and binder gel varied for each sample. Based on dry weight, the amount of the active material varied between 40–50%, 50–60%, or 60–70%; Super P between 10–15%, 15–25%, or 25–40%; CNF between 1–5%, 5–10%, or 10–15%; and the binder between 10–15%, 15–20%, or 20–30%. The concentration of the slurry was checked midway through the ball milling process, and additional solvent was added if necessary.

[0604] The cathode slurry was prepared by mixing the active material cathode powder, namely lithium nickel manganese cobalt oxide (NCM), with a PVDF binder solution and a carbon conductor in a ball mill operated at 250 rpm for 3 hours. The active material cathode powder, carbon conductor, and PVDF binder were mixed in a ratio of 85:10:5 by dry weight. During the ball milling process, the concentration of the slurry was checked, and more solvent was added if necessary.

[0605]

[0606] [Experimental Example 3] Electrochemical Impedance Analysis

[0607] EIS is a powerful diagnostic tool that can be used to characterize limits and improve fuel cell performance. The three fundamental causes of voltage loss in fuel cells are charge transfer activation or "kinetic" losses, ion and electron transfer or "resistance" losses, and concentration or "mass transfer" losses. Among these factors, EIS is an experimental technique that can be used to isolate and quantify these polarization sources. Qualitative and quantitative information regarding impedance sources within the fuel cell can be extracted by applying a physically sound equivalent circuit model in which the physicochemical processes occurring within the fuel cell are represented as a network of resistors, capacitors, and inductors. EIS is useful for product verification and quality assurance in manufacturing operations, as well as for the research and development of new materials and electrode structures.

[0608] During impedance measurement, a Frequency Response Analyzer (FRA) is used to apply a small-amplitude AC signal to the battery through a load. The battery's AC voltage and current responses are analyzed by the FRA to determine the cell's resistive, capacitive, and inductive behavior, as well as its impedance, at specific frequencies. Physicochemical processes occurring within the cell, such as electron and ion transfer, liquid and solid phase reactant transfer, and heterogeneous reactions, exhibit different characteristic time constants and therefore appear at different AC frequencies.

[0609] When performed over a wide range of frequencies, impedance spectroscopy can be used to identify and quantify the impedance associated with these various processes.

[0610] Equivalent circuit modeling of EIS data is used to extract physically meaningful characteristics of electrochemical systems by modeling impedance data in terms of an electrical circuit composed of ideal resistors (R), capacitors (C), and inductors (L). Since the processes occurring are distributed across time and space, actual systems do not necessarily behave ideally; therefore, special circuit components are frequently used. These include generalized constant phase devices (CPE) and Warburg devices (ZW). Warburg devices are used to represent the diffusion or mass transfer impedance of a cell.

[0611] In an equivalent circuit, resistance represents the conductive path for ion and electron transfer. As such, it represents the bulk resistance of a material to charge transfer, such as the resistance of an electrolyte to ion transfer or the resistance of a conductor to electron transfer.

[0612] Resistance is also used to represent the resistance to the charge transfer process at the electrode surface. Capacitors and inductors are related to the space charge polarization region, such as an electrochemical double layer, and the adsorption / desorption processes at the electrodes, respectively.

[0613] EIS data for electrochemical cells, such as fuel cells, are mostly displayed as Nyquist and Bode plots. A Bode plot represents the magnitude of impedance (or the real or virtual component of impedance) and the phase angle as a function of frequency.

[0614] Since impedance and frequency often span tens of times, they are frequently displayed on a logarithmic scale. Bode plots explicitly show the frequency dependence of the impedance of the device under test.

[0615] A composite plane or Nyquist plot represents a virtual impedance that indicates the capacitive and inductive characteristics of a cell relative to its actual impedance. The Nyquist plot has the advantage that activation control processes with inherent time constants appear as inherent impedance arcs, and the shape of the curve provides insight into possible mechanisms or governing phenomena. However, this format for representing impedance data has the disadvantage of inherent frequency dependence; therefore, the AC frequency of selected data points must be indicated. Since both data formats have advantages, it is generally best to display both Bode and Nyquist plots.

[0616]

[0617] [Experimental Example 4] Measurement of Other Electrochemical Performance

[0618] The electrochemical performance of the binder was evaluated using pouch-type cells. Electrodes for electrochemical evaluation were fabricated by coating anode and cathode slurries onto copper and aluminum foils using glass rods. The coated copper or aluminum foils were then dried in a vacuum oven at 60°C for 8 hours. The electrodes were kept inside a glove box filled with argon for 12 hours to degas. A Celgard 2325 microporous polypropylene / polyethylene / polypropylene three-layer membrane was used as a separator. The fabricated battery pouch cells were used in constant current charge-discharge tests performed with a battery test system (Neware CT-3008W).

[0619] Cyclic voltammetry was performed on the battery cells using an Autolab PGSTAT100 electrochemical workstation. The scan range was 2.0–4.8 V, and the scan rate was 0.1 mV s⁻¹ unless otherwise specified. Electrochemical impedance spectroscopy (EIS) was performed on the battery cells using an Autolab PGSTAT 100 electrochemical workstation equipped with an EIS module. The frequency range was 1 MHz to 10 Hz, and the amplitude was 5 mV. Prior to testing, each cell was relaxed for at least 4 hours to reach equilibrium.

[0620]

[0621] [Experimental Example 5] Electrochemical Performance

[0622] Pouch cells were assembled, and all Si / NCM811 full cells were cycled at 0.1C between 2.5-3.7 V. In addition, to verify the rate capability characteristics of the electrodes, the capacitance of each electrode was measured by setting it to 1C, 2C, 3C, 4C, and 5C, and finally returning it to 1C.

[0623] As shown in Figure 1, the test results indicate that the scaffold anode exhibits the highest performance compared to Si-C-CNF-Chitosan TPP and Si-C-CNF-Chitosan when cycling at a rate of 0.1C in a Si / NCM811 full cell.

[0624] After 200 cycles, the Si-C-CNF-Chitosan TPP scaffold and Si-C-CNF-Chitosan TPP anode retained 94% and 93% of their initial discharge capacities, respectively, while the Si-C-CNF-Chitosan anode retained only 92% of its initial capacity. This indicates that the superior performance of the scaffold anode over a large number of cycles is attributed to its porous elastic structure, while maintaining the excellent bonding characteristics of the chitosan TPP binder. Freeze-drying can significantly improve the cycle stability of the Si electrode by introducing cavities (voids) that allow Si particles to expand with minimal deformation of the electrode structure. Additionally, the scaffold structure can enhance rate capability because the porous structure increases ion transport in the electrode and accelerates charge transfer reaction motion through the enhanced surface area.

[0625] In addition, to verify the rate characteristics of the binder-applied electrode, electrochemical evaluations were performed at 1C, 2C, 3C, 4C, and 5C, followed by recovery to 1C. As shown in Figure 3, the Si-C-Chitosan-TPP-CNF anode exhibited high capacity retention at all C-rates, and notably at 5C, showed a capacity retention approximately twice that of conventional chitosan. It demonstrates excellent performance due to the enhanced adhesion of chitosan TPP. In contrast, PVDF showed a very low capacity retention of 4% at 5C due to weak van der Waals bonding.

[0626] To further understand the charge transfer and Li ion diffusion behavior within the electrode, electrochemical impedance spectroscopy (EIS) measurements were performed after the 200th cycle. As shown in Fig. 4, the Nyquist plots of the EIS measurements performed for both the Si-C-chitosan TPPCNF scaffold and the Si-C-chitosan TPP-CNF anode consist of two overlapping semicircles in the high and mid-frequency regions and a straight line of Warburg impedance in the low-frequency region.

[0627] The Nyquist plot after the first cycle shows that the two anodes are similar to charge transfer resistance (Rct) in the initial stage.

[0628] After 200 cycles, the Rct of the Si-C-Chitosan TPP-CNF anode was found to be relatively higher (138 mΩ) compared to the Si-C-Chitosan TPP-CNF scaffold anode (126 mΩ), but both values ​​are significantly smaller than the Rct previously reported by scientists for Si-based anodes using PVDF or other polymer binders. The low Rct after 200 cycles indicates that the conductivity and mechanical integrity of the electrode are maintained without polarization by providing a rigid matrix structure that helps maintain contact between silicon and the conductor and preserve the integrity of the anode. The lower Rct for the Si-C-Chitosan TPP-CNF scaffold anode compared to the Si-C-Chitosan TPP-CNF anode after 200 cycles demonstrates that Li ion transport within the scaffold structure is more fluid, as it provides a clear pathway for Li ions to migrate and bind with Si nanoparticles.

[0629]

[0630] Although the embodiments have been described above with reference to limited examples and drawings, those skilled in the art can make various modifications and variations from the description above. For example, suitable results may be achieved even if the described techniques are performed in a different order than described, and / or the described components are combined or assembled in a form different from described, or replaced or substituted by other components or equivalents. Therefore, other implementations, other embodiments, and equivalents to the claims below are also within the scope of the claims.

Claims

1. A chitosan polymer compound selected from the group consisting of the following chemical formulas 1 to 7: [Chemical Formula 1] [Chemical Formula 2] [Chemical Formula 3] [Chemical Formula 4] [Chemical Formula 5] [Chemical Formula 6] [Chemical Formula 7] In the above chemical formulas 1 to 7, The above X1 and X2 is selected from electron-withdrawing functional groups composed of hydrogen, -SO2CF3, -COCF3, -SO2CN, -CF3, and -CN, respectively, and Y is hydrogen or -COOH, and R1, R2, R3, and R4 are identical or different from one another and each independently have a hydrogen atom, a substituted or unsubstituted C1 to C5 alkyl or -(CH2) p -COOX 1 (p is 1 to 5, and X 1 It is an alkali metal, and R5, R6, R7 and R8 are identical or different from each other and are each independently H or COOH, at least one of R5, R6, R7 and R8 is COOH, and m, n and o are each integers from 10 to 10,000.

2. In Paragraph 1, The above chemical formulas 1 to 7 are compounds selected from the following compounds. , . , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , .

3. A mixture of a novel chitosan polymer compound represented by Chemical Formulas 1 to 7 and a novel electrically conductive polymer compound selected from Chemical Formulas 8 to 9. [Chemical Formula 8] [Chemical Formula 9] The above X is selected from electron-withdrawing functional groups selected from -SO2CF3, -COCF3, -SO2CN, -CF3, and -CN; and Y is selected from hydrogen and -COOH, and R1, R 10 , R 11 , R 12 is a linear or branched C1 to C20 alkyl group or a C2 to C20 alkenyl group, and m and n are integers from 10 to 10,000.

4. The binder according to claim 1, comprising a compound selected from the compounds of chemical formulas 1 to 7.

5. In claim 4, the binder comprises 0.01 to 80 weight% of any one or more compounds selected from the compounds of Formulas 1 to 7 or a mixture thereof, based on 100 weight% of the total binder.

6. A binder according to claim 3, comprising a mixture of a novel chitosan polymer compound represented by chemical formulas 1 to 7 and a novel electrically conductive polymer compound represented by chemical formulas 8 to 9.

7. In claim 6, the binder comprises a mixture of a novel chitosan polymer compound represented by Chemical Formulas 1 to 7 and a compound selected from Chemical Formulas 8 to 9, in an amount of 0.01 to 80 weight% based on 100 weight% of the total binder.

8. An electrode for a secondary battery manufactured using the binder of Chemical Formulas 1 to 7 in claim 4.

9. A battery manufactured using the binder of paragraph 4 or 6.

10. A battery made reusable by using the binder of paragraph 4 or 6.

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