Battery electrode components

Abstract

This invention provides an improved composition for preparing electrodes for rechargeable batteries. [Solution] The present invention relates to a composition, the composition being (a) a polymer, (i) a polyamine core comprising a plurality of amine groups and comprising the structure of formula (I), TIFF2026521806000009.tif32170, R 1 H is part of the polyamine core, R 2 H or an organic group, R 3 is H or an organic group, however R 2 and R 3 The composition comprises (ii) a polymer having a plurality of polyester segments bonded to a polyamine core via ionic bonds, and (b) an electrically conductive carbon-based material, wherein at least one of the elements is H, and the weight ratio of polymer (a) to electrically conductive carbon-based material (b) in the present invention is in the range of 70:100 to 3:100.

Description

Technical Field

[0001] The present invention relates to a composition comprising a polymer and a conductive carbon-based material, the use of the composition for preparing an electrode for a rechargeable battery, a method for manufacturing a rechargeable battery electrode, a battery electrode, and a rechargeable battery.

Background Art

[0002] WO 2021 / 028519 describes a dispersant comprising a polyester derived from a poly(lactone) and an amine, and having an acid value of less than 15 mg KOH / g. This document also describes the use of the dispersant in a composition for a rechargeable lithium-ion battery electrode. The dispersant described in this document has been found not to provide satisfactory results in the dispersion of conductive carbon-based materials.

[0003] US 9,574,121 B2 relates to a process for preparing an amine adduct by reacting a polyamine component, a polyester component, and an epoxide functional component. The amine adduct is suitable as a wetting agent and a dispersant, particularly in coating and plastic applications.

Summary of the Invention

Problems to be Solved by the Invention

[0004] There is a continuing need for an improved composition for preparing an electrode for a rechargeable battery, particularly a composition comprising a low-viscosity conductive carbon-based material.

Means for Solving the Problems

[0005] The present invention provides a composition comprising: (a) a polymer having: (i) a polyamine core containing a plurality of amine groups and having the structure of formula (I), [[ID=H is part of the polyamine core, and R 2 is H or an organic group, R 3 is H or an organic group, provided that at least R 2 or R 3 One of these is H. (ii) A plurality of polyester segments bonded to the polyamine core via ionic bonds, (b) Conductive carbon-based material, Here, the weight ratio of polymer (a) to conductive carbon-based material (b) in the composition of the present invention is in the range of 70:100 to 3:100.

[0006] As described above, the polymer of the composition of the present invention comprises a polyamine core. Suitable examples of polyamine cores include diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine, hexaethyleneheptamine, and higher-order homologs, with the general formula NH2-(C2H4NH) n These include higher-order linear condensates of C2H4-NH2 with n>5, such as dipropylenetriamine, (3-(2-aminoethyl)aminopropylamine, N,N-bis(3-aminopropyl)methylamine, tetramethyliminobispropylamine, N,N-dimethyldipropylenetriamine, bis-(3-dimethylaminopropyl)amine, and N,N′-bis(3-aminopropyl)-ethylenediamine.

[0007] Suitablely, the polyamine core is an organic polyamine compound containing, on average, at least two, preferably 6 to 600, tertiary amino groups.

[0008] Tertiary amino groups typically result in good adsorption to solid surfaces and are less likely to cause undesirable reactions. Furthermore, tertiary amino groups enable high molecular weight structures, while maintaining relatively low viscosity.

[0009] Typically, branched aliphatic polyamines, particularly poly(C2-C4)-alkyleneamines having primary, secondary, and tertiary amino groups, are used. A particularly preferred polyamine core is polyethyleneimine. Polyethyleneimines are commercially available under trademark names such as BASF's Lupasol™ and Nippon Shokubai's Epomin™. These are produced by known methods, for example, by polymerization of ethyleneimine.

[0010] Typically, the molar ratio of primary to secondary amino groups in a polyamine core is in the range of 1:1 to 1:5. Generally, the molar ratio of primary to tertiary amino groups is in the range of 3:1 to 1:3.

[0011] In a typical embodiment, the weight-average molecular weight of the polyamine core is in the range of 200 to 200,000, preferably 250 to 40,000, and particularly preferably 300 to 25,000 g / mol.

[0012] If the molecular weight is too low, adsorption to solid surfaces may be weak, and if the molecular weight is too high, problems may arise in terms of handling and solubility. The weight-average molecular weight of the polyamine core can be appropriately determined using light scattering.

[0013] The polyamine core contains a structure according to formula (I). A polyamine core having a structure according to formula (I) is appropriately prepared by the reaction of a polyamine with a compound having at least one epoxide group. Preferably, the compound having at least one epoxide group has 3 to 25 carbon atoms. More preferably, the compound has 4 to 20 carbon atoms. Particularly preferred is the use of an epoxide compound having one epoxide group per molecule.

[0014] Suitable compounds having at least one epoxide group are glycidyl ethers, glycidyl esters, epoxidized olefins, and more preferably, epoxidized α-olefins.

[0015] Preferred glycidyl ethers are glycidyl ethers having a C2-C30 hydrocarbyl group bonded to an ether atom. The hydrocarbyl group can be aliphatic (including alicyclic), aromatic, or aral-aliphatic, and can be linear or branched, saturated or unsaturated. Preferably, the group is selected from C4-C24 aliphatic groups and substituted or unsubstituted phenyl groups. Very preferably, the group is selected from saturated C6-C18 aliphatic groups, such as C8-C16 alkyl groups. Suitable examples include n-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, C8-C10 aliphatic glycidyl ether, C12-C14 aliphatic glycidyl ether, C13-C15 alkyl glycidyl ether, oleyl glycidyl ether, allyl glycidyl ether, cresyl glycidyl ether, p-tert-butylphenyl glycidyl ether, nonylphenyl glycidyl ether, phenyl glycidyl ether, and naphthyl glycidyl ether. Preferred examples include 2-ethylhexylglycidyl ether, C12-C14 aliphatic glycidyl ether, and C13-C15 alkylglycidyl ether.

[0016] Preferred glycidyl esters are those having a C2-C30 hydrocarbyl group bonded to the ester group. The hydrocarbyl group can be aliphatic (including alicyclic), aromatic, or aral-aliphatic, and can be linear or branched, saturated or unsaturated. Preferably, the group is selected from C4-C24 aliphatic groups and substituted or unsubstituted phenyl groups. Very preferably, the group is selected from saturated C6-C18 aliphatic groups, such as C8-C16 alkyl groups.

[0017] Appropriate examples include 2-ethylhexylglycidyl esters and glycidyl esters of neodecanoic acid.

[0018] Preferred epoxidized olefins are based on α-olefins containing 4 to 30 carbon atoms. The hydrocarbyl group bonded to the epoxy group may be aliphatic (including alicyclic), aromatic, or araliphatic, and may be linear or branched. Preferably, the group bonded to the epoxy group is selected from C4-C24 aliphatic groups and substituted or unsubstituted phenyl groups. Very preferably, the group is selected from saturated C6-C18 aliphatic groups, such as C8-C16 alkyl groups.

[0019] Suitable examples of epoxidized olefins include 1,2-hexene oxide, 1,2-octene oxide, 1,2-nonene oxide, 1,2-undecene oxide, 1,2-dodecene oxide, 1,2-octadecene oxide, 4-methyl-1,2-pentene oxide, 1,2-butene oxide, styrene oxide, butadiene monooxide, isoprene monooxide, cyclopentene oxide, 2-ethyl-1,2-butene oxide.

[0020] Preferably, in formula (I), R 2 and R 3 are organic groups that are hydrocarbyl groups or organic groups containing an ether group or an ester group. Since ring-opening of the oxirane group occurs during the reaction of polyethyleneimine with the epoxide, either R 2 or R 3 in formula (I) is a hydrogen atom.

[0021] When the nitrogen atom in structure (I) is a secondary amine, R 1 is hydrogen. The secondary amine may be further modified with a compound having at least one epoxide group. In that case, the reaction process converts the secondary amine to a tertiary amine, and R 1 is.

[0022]

Chemical formula

[0023] Furthermore, polyethyleneimines may contain non-terminal secondary amine groups. When these groups react with epoxide groups, R 1 A polyethyleneimine of structure (I), in which R is part of the polyethyleneimine, is formed. 1 It contains at least one repeating unit which includes one nitrogen atom and two CH2 groups.

[0024] In preferred embodiments, the polyamine core is a reaction product of polyethyleneimine and at least one compound having at least one epoxide group, where the molar ratio of the total amine groups of polyethyleneimine to the epoxide groups derived from the compound having at least one epoxide group is in the range of 100.0:30.0 to 100.0:0.3, preferably in the range of 100.0:20.0 to 100.0:1.0, more preferably in the range of 100.0:15.0 to 100.0:2.0, most preferably in the range of 100.0:13.0 to 100.0:3.0, for example, in the range of 100.0:10.0 to 100.0:4.0.

[0025] In another preferred embodiment, the polyamine core is a reaction product of polyethyleneimine and at least one compound having at least one epoxide group, wherein the molar ratio of the primary amine group of polyethyleneimine to the epoxide group derived from the compound having at least one epoxide group is in the range of 100.0:80.0 to 100.0:1.0, preferably in the range of 100.0:50.0 to 100.0:3.0, more preferably in the range of 100.0:40.0 to 100.0:6.0, and most preferably in the range of 100.0:35.0 to 100.0:8.0, for example, in the range of 100.0:30.0 to 100.0:10.0.

[0026] As described above, the polymer comprises multiple polyester segments bonded to a polyamine core via ionic bonds.

[0027] Suitable polyester segments can be prepared by reacting dicarboxylic acids and their esterifiable derivatives, such as anhydrides, acid chlorides, or dialkyl esters, such as dimethyl or diethyl esters, with diols and monofunctional carboxylic acids. If necessary, the formation of dihydroxypolyesters can be suppressed by using the corresponding stoichiometric amount of monofunctional carboxylic acid. Esterification can be carried out in bulk or by azeotropic esterification in the presence of an entraining agent. Such condensation reactions are carried out at temperatures, for example, about 50°C to 250°C. Examples of dicarboxylic acids that can be used in this method include succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, sebacic acid, pimelic acid, phthalic acid, or dimerized fatty acids and their isomers and their hydrogenation products.

[0028] Examples of diols that can be used in this method include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, cis-1,2-cyclohexanedimethanol, trans-1,2-cyclohexanedimethanol, and polyglycols based on ethylene glycol and / or propylene glycol. The corresponding monofunctional carboxylic acid used as a starting component preferably has 1 to 42, particularly 4 to 18, preferably 8 to 14 carbon atoms and may be saturated or unsaturated, aliphatic or aromatic, linear, branched and / or cyclic. Examples of suitable corresponding monofunctional carboxylic acids include stearic acid, isostearic acid, oleic acid, lauric acid, and benzoic acid. Additional suitable acids are tertiary monofunctional carboxylic acids, also known as Koch acids, such as 2,2-dimethylpentanoic acid, tert-nonanoic acid, and neodecanoic acid. This type of Cochic acid is also known commercially as Versatic® acid (Shell), Neo-acids (Exxon), or Secanoic acid (Kuhlmann). Versatic® acids are named according to the total number of carbon atoms in the molecule. Suitable examples include Versatic® acids 5, 6, 9, and 10.

[0029] The polyester segment appropriately contains at least 5, preferably 6 to 70, ester groups. In yet another embodiment, the polyester segment additionally contains ether groups.

[0030] The polyester segment is bonded to the polyamine core via ionic bonds. To form ionic bonds between the polyamine core and the polyester segment, the polyester segment preferably contains carboxylic acid groups. The carboxylic acid groups of the polyester segment readily form salts with amine groups present in the polyamine core, thereby bonding the polyamine core to the polyester segment via ionic bonds. In preferred embodiments, the average number of carboxylic acid groups in the polyester segment is in the range of 0.9 to 1.5. The carboxylic acid groups can exist as terminal or side-chain groups. Terminal carboxylic acid groups are preferred.

[0031] When the carboxylic acid functionality exceeds 1.5, crosslinking may occur, which typically leads to decreased solubility, reduced compatibility, excessive viscosity, or poor compatibility.

[0032] Particularly suitable polyester segments can be obtained by polycondensation of one or more optionally alkyl-substituted hydroxycarboxylic acids, e.g., ricinoleic acid or 12-hydroxystearic acid, and / or by ring-opening polymerization of the corresponding lactones, e.g., propiolactone, valerolactone, and caprolactone. Therefore, the polyester segments preferably contain repeating units of the formula -[-O-(CH2)nC(=O)]-, where n is an integer in the range of 3 to 6. Lactone polymerization is carried out using known methods, for example, initiated with p-toluenesulfonic acid or dibutyltin dilaurate at a temperature of about 50°C to 200°C. Particularly preferred are polyesters based on ε-caprolactone, which are optionally used in combination with δ-valerolactone.

[0033] Often, at least 50% by weight, preferably 70 to 100% by weight, of the polyester segment is a linear, monocarboxylic acid-functionalized caprolactone polyester. The polyester segment appropriately has a weight-average molecular weight in the range of 500 to 10,000 g / mol, preferably 800 to 8,000 g / mol.

[0034] When the weight-average molecular weight is less than 500 or greater than 10,000, general compatibility is often compromised.

[0035] Number average molecular weight M n and weight-average molecular weight M w This can be determined by gel permeation chromatography (GPC) according to DIN 55672 Part 3 [2016-03].

[0036] As described above, the polyester segments of the polymer are bonded to the polyamine core via ionic bonds. In a preferred embodiment, the polymer further comprises polyester segments bonded to the polyamine core via amide groups.

[0037] In exemplary embodiments, 10–40% of the polyester segments are bonded to the polyamine core via amide groups, and 90–60% are bonded to the polyamine core via ionic bonds. The ratio of polyester segments bonded to the polyamine core via ionic and amide bonds can be controlled by the temperature at which the polyamine core and polyester segments react. Relatively low temperatures in the range of 60–100°C promote the formation of ionic bonds. Relatively high temperatures above 120°C promote the formation of amide bonds in addition to ionic bonds.

[0038] The polymer used in the composition of the present invention is appropriately prepared in a two-step process. In the first step, a polyamine reacts with a compound having at least one epoxide group. Preferably, the polyamine has at least one amino group selected from primary and secondary amino groups. The compound having at least one epoxide group preferably has one epoxide group. The polyamine compound and the compound having at least one epoxide group are mixed and reacted at a temperature in the range of 60 to 150°C until all epoxide groups have substantially reacted to form a polyamine core. Generally, the reaction time is in the range of 30 to 300 minutes. In the second reaction step, the polyamine core reacts appropriately with a polyester segment, generally a polyester segment having a carboxylic acid group. The polyamine core and the polyester segment react appropriately by mixing and heating at a temperature in the range of 60 to 150°C, preferably 80 to 140°C. The appropriate reaction time is in the range of 30 to 300 minutes. The polyester segment is prepared in the manner described above according to generally known methods. The preparation of suitable polymers for use in the compositions of the present invention is also described in the Examples section of US9574121B2.

[0039] The composition of the present invention further comprises a conductive carbon-based material (carbon-based material). The carbon-based material is a material in which carbon accounts for 90-100% by weight. A carbon-based material is selected for use in the field of battery electrode manufacturing, and it is conductive. Examples of suitable conductive carbon-based materials include carbon black, carbon nanotubes, graphite, carbon fibers, graphene, fullerenes, and mixtures thereof. Preferred carbon-based materials are carbon black, graphene, and carbon nanotubes.

[0040] Generally, the weight ratio of polymer (a) to conductive carbon-based material (b) in the composition of the present invention is in the range of 70:100 to 3:100, preferably in the range of 50:100 to 5:100, and most preferably in the range of 30:100 to 7:100.

[0041] The composition of the present invention is intended to be used for manufacturing electrodes for rechargeable batteries. Accordingly, the composition appropriately comprises a cathode active material for rechargeable batteries.

[0042] In the cathode of lithium-ion rechargeable batteries, lithium-containing transition metal oxides or lithium metal phosphates (e.g., LiFePO4) are generally used as cathode active materials. Preferably, a compound is used that mainly contains lithium and at least one transition metal element selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Mo, and W, with a molar ratio of lithium to the transition metal element of 0.3 to 2.2. More preferably, a compound is used that mainly contains lithium and at least one transition metal element selected from the group consisting of V, Cr, Mn, Fe, Co, and Ni, with a molar ratio of lithium to the transition metal of 0.3 to 2.2. It should be noted that Al, Ga, In, Ge, Sn, Pb, Sb, Bi, Si, P, B, etc. may be present in a molar ratio of less than 30 mol% relative to the mainly present transition metal. Among the active materials described above, the general formula Li x MO2 (where M represents at least one of Co, Ni, Fe, or Mn, and x is between 0 and 1.2), or Li y It is preferable to use at least one material having a spinel structure represented as N2O4 (where N contains at least Mn and y is between 0 and 2).

[0043] Furthermore, Li is particularly preferred as the cathode active material. y M a D 1-a At least one material containing O2 (where M represents at least one of Co, Ni, Fe, and Mn, and D represents at least one of Co, Ni, Fe, Mn, Al, Zn, Cu, Mo, Ag, W, Ga, In, Sn, Pb, Sb, Sr, B, and P, except the element corresponding to M is excluded, with y=0~1.2 and a=0.5~1), and Li z (N b E 1-bIt is particularly preferable to use materials having a spinel structure represented as )2O4(where N represents Mn, E represents at least one of Co, Ni, Fe, Mn, Al, Zn, Cu, Mo, Ag, W, Ga, In, Sn, Pb, Sb, Sr, B, and P, with b=1~0.2 and z=0~2).

[0044] Specifically, Li x CoO2, Li x KiO2, Li x MnO2, Li x Co a Ni 1-a O2, Li x Co b V 1-b O z Li x Co b Fe 1-b O2, Li x Mn2O4, Li x Mn c Co 2-c O4, Li x Mn c Ni 2-c O4, Li x Mn c V 2-c O4, Li x Mn c Fe 2-c Examples include O4 (x=0.02~1.2, a=0.1~0.9, b=0.8~0.98, c=1.6~1.96, z=2.01~2.3). The most preferred lithium-containing transition metal oxide is Li x CoO2, Li x KiO2, Li x MnO2, Li x Co a Ni 1-a O2, Li x Mn2O4, Li x Co b V 1-b O z (x=0.02~1.2, a=0.1~0.9, b=0.9~0.98, z=2.01~2.3) are examples. It should be noted that the value of x can increase or decrease depending on charging and discharging.

[0045] The average particle size of the cathode active material is not particularly limited, but a size of 0.1 to 50 μm is preferred. It is preferable that the volume of particles between 0.5 and 30 μm accounts for 95% or more. It is more preferable that the volume occupied by the group of particles with a particle diameter of 3 μm or less accounts for 18% or less of the total volume, and it is even more preferable that the volume occupied by the group of particles between 15 μm and 25 μm accounts for 18% or less of the total volume.

[0046] In a preferred embodiment, the cathode active material comprises at least one of lithium nickel cobalt aluminum oxide and lithium nickel manganese cobalt oxide.

[0047] The composition of the present invention is preferably liquid or paste-like at a temperature of 20°C. This facilitates the preparation of electrodes from the composition. To make the composition liquid or paste-like, the composition preferably further contains at least one organic solvent in an amount of 10 to 90% by weight, calculated based on the total weight of the composition.

[0048] Generally, an organic solvent capable of dissolving the polymer or oligomer components of the composition is selected. The organic solvent may also include multiple types of organic solvents, such as a mixture of two or more solvents.

[0049] Examples of suitable solvents include ester solvents such as methyl acetate, ethyl acetate, γ-butyrolactone, and ε-caprolactone; ether solvents such as dibutyl ether and tetrahydrofuran; ketone solvents such as cyclohexanone; aromatic hydrocarbon solvents such as benzene, toluene, and fluorobenzene; carbonate solvents such as dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (MEC), ethyl methyl carbonate (EMC), ethylene carbonate (EC), and propylene carbonate (PC); alcohol solvents such as ethyl alcohol and isopropyl alcohol; nitriles such as R-CN (where R is a linear, branched, or cyclic C2-C20 hydrocarbon group, which may include a double-bonded aromatic ring or ether bond); amides such as dimethylformamide; dioxolanes such as 1,3-dioxolane; or sulfolanes, which can be used as organic solvents. Further examples of suitable solvents include aprotic bipolar solvents such as dimethyl sulfoxide, dimethylformamide, or N-methylpyrrolidone, or other solvents containing an amide group. When water is used as the solvent, it is preferable to further include a thickening agent. The amount of solvent is adjusted so that a viscosity is obtained in which the paste can be easily applied to the current collector.

[0050] Generally, the solvent is present in the composition of the present invention in an amount of 10 to 90% by weight, preferably 20 to 80% by weight, calculated relative to the total weight of the composition.

[0051] In a more preferred embodiment, the composition further comprises a polymer binder. The binder improves the adhesion between positive electrode active material particles and the adhesion between the positive electrode active material and the current collector. Examples of binders include fluorinated polymers such as polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, and polytetrafluoroethylene; rubber binders such as styrene-butadiene rubber (SBR), ethylene-propylene-diene monomer rubber (EPDM), sulfonated EPDM, and fluororubber; and binders based on polyethylene, polypropylene, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylonitrile, carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, and polyacrylate. If necessary, the binder may be used in the form of an aqueous dispersion.

[0052] The appropriate amount of binder to use is 1.0 to 50.0 parts by mass per 100 parts by mass of the non-volatile substance of the composition, and more particularly, the amount used is about 1.0 to 20.0 parts by mass, more preferably 1.0 to 10.0 parts by mass of the non-volatile substance of the composition.

[0053] The compositions of the present invention are very suitable for preparing electrodes for rechargeable batteries. Therefore, the present invention also relates to the use of the compositions of the present invention for preparing electrodes for rechargeable batteries, and to a process for preparing rechargeable electric battery electrodes using the compositions of the present invention. Preferably, the electrode is a cathode.

[0054] The compositions of the present invention can be prepared, for example, by mixing the components to prepare a paste or slurry by kneading. A solvent can be used during kneading.

[0055] Examples of solvents include known solvents such as dimethylformamide and isopropanol, toluene and N-methylpyrrolidone in the case of fluorinated polymers, and water in the case of SBR. When using water as a solvent for a binder, it is preferable to use a thickening agent in the composition. The amount of solvent is adjusted to obtain a viscosity that allows the paste to be easily applied to the current collector.

[0056] The electrodes can be formed from the molding of the electrode paste described above. For example, the electrodes can be obtained by applying the electrode paste to a current collector, drying it, and then pressure molding it.

[0057] Examples of current collectors include foils and meshes made of aluminum, nickel, copper, stainless steel, etc. The paste coating thickness is generally 40 to 200 μm. There are no particular restrictions on the paste coating method, and examples of coating methods include coating with a doctor blade or bar coater, followed by shaping with a roll press or the like.

[0058] Examples of pressure forming include roll pressure forming and compression forming. The pressure used in pressure forming is approximately 1-3 t / cm². 2 This is preferable. Generally, increasing the electrode density increases the battery capacity per unit volume. However, if the electrode density increases too much, the cycle characteristics generally deteriorate. When using electrode paste in the preferred embodiment of the present invention, the deterioration of cycle characteristics is small even when the electrode density increases. Generally, the electrode density is 1.0 to 4.0 g / cm³. 3 The range is as follows. In some embodiments, the electrode density of the cathode is 2.0 to 3.5 g / cm³. 3 It is in the range of 1.2-2.0 g / cm³, and the anode density is 1.2-2.0 g / cm³. 3 It is within the range.

[0059] The present invention further relates to a battery electrode comprising the composition of the present invention, and a rechargeable battery comprising said electrode. The term "battery" includes a single electrochemical cell comprising an electrode, a separator, and an electrolyte, as well as a collection of cells or a cell assembly.

[0060] In lithium-ion rechargeable batteries, a separator is sometimes provided between the cathode and the anode. Examples of separators include nonwoven fabrics, cloths, microporous films, and combinations thereof, each primarily composed of polyolefins such as polyethylene and polypropylene.

[0061] The present invention further relates to the use of a polymer having the following for the preparation of a composition for manufacturing electrodes for rechargeable batteries: (i) A polyamine core comprising multiple amine groups and having the structure of formula (I), [ka] R 1 H is part of the polyamine core, and R 2 is H or an organic group, R 3 is H or an organic group, however R 2 and R 3 At least one of them is H, (ii) Multiple polyester segments bonded to the polyamine core via ionic bonds [Example 1]

[0062] Polyester 1 140.00 g (0.67 mol) of lauric acid and 797.78 g (6.99 mol) of epsilon-caprolactone were added to a four-neck flask and heated to 90°C. 0.47 g of tetra-n-butylzirconate was added. The reaction mixture was held at 90°C for 4 hours, then heated to 190°C and held at this temperature for 1 hour. The material was then cooled to room temperature. The theoretically calculated molecular weight of the polyester is 1400 g / mol.

[0063] Polyester 2 101.55 g (0.51 mol) of lauric acid and 927.96 g (8.13 mol) of ε-caprolactone were added to a four-neck flask and heated to 90°C. 0.47 g of tetra-n-butyl zirconate was added. The reaction mixture was held at 90°C for 4 hours, then heated to 190°C and held at this temperature for 1 hour. The material was then cooled to room temperature. The theoretically calculated molecular weight of the polyester is 2028 g / mol.

[0064] Polyester 3 101.55 g (0.51 mol) of lauric acid, 203.35 g (2.04 mol) of γ-valerolactone, and 694.60 g (6.09 mol) of ε-caprolactone were added to a four-neck flask and heated to 90°C. Then, 0.47 g of tetra-n-butylzirconate was added. The reaction mixture was held at 90°C for 4 hours, then heated to 190°C and held at this temperature for 1 hour. The material was then cooled to room temperature. The theoretically calculated molecular weight of the polyester is 1970 g / mol.

[0065] Preparation of polymers having a polyamine core and multiple polyester segments Raw materials used: PEI 1 = Polyethyleneimine 10,000 g / mol, Epomin SP200, Nippon Shokubai PEI 2 = Polyethyleneimine 2000g / mol, Lupasol PR 8515, BASF PEI 3 = Polyethyleneimine 1300g / mol, Lupasol G 20, BASF

[0066] Comparative Example 1 7.0 g (0.0007 mol) of PEI 1 and 93.0 g (0.0694 mol) of polyester 1 were added to a four-neck flask, heated to 150°C, and held at this temperature for 5 hours. The reaction mixture was then cooled to room temperature. The acid value was 24.1 mg KOH / g, which corresponds to 66.5% of the polyester segment bonded to the polyamine core via ionic bonds.

[0067] Example 1 7.0 g (0.0007 mol) of PEI 1 was added to a 4-neck flask and heated to 110°C. 0.9 g (0.0056 mol) of cresylglycidyl ether was added and homogenized. The mixture was heated to 130°C and 93.00 g (0.0694 mol) of polyester 1 was added. The mixture was held at this temperature for 3 hours, and then the reaction mixture was cooled to room temperature. The acid value was 31.1 mg KOH / g. This corresponds to 87.6% of the polyester segment bonded to the polyamine core via ionic bonds.

[0068] Comparative Example 2 24.00 g (0.01201 mol) of PEI 2 was added to a 4-neck flask and heated to 80°C. 72.00 g (0.03599 mol) of polyester 2 and 24.00 g (0.01201 mol) of polyester 3 were added. The mixture was heated to 120°C and held at this temperature for 3 hours, after which the reaction mixture was cooled to room temperature. The acid value was 22.4 mg KOH / g, which corresponds to 87.6% of the polyester segment ionically bonded to the polyamine core.

[0069] Example 2 8.39 g (0.0042 mol) of PEI 2 was added to a 4-neck flask and heated to 110°C. 11.62 g (0.05095 mol) of glycidyl neodecanoate was slowly added and homogenized for 0.5 hours. Then, 25.17 g (0.01258 mol) of polyester 2 and 8.39 g (0.0042 mol) of polyester 3 were added. The mixture was heated to 130°C and held at this temperature for 3 hours, after which the reaction mixture was cooled to room temperature. The acid value was 16.3 mg KOH / g. This corresponds to 92.6% of the polyester segment bonded to the polyamine core via ionic bonds.

[0070] Example 3 7.00 g (0.0007 mol) of PEI 1 was added to a 4-neck flask and heated to 110°C. 2.52 g (0.0111 mol) of glycidyl neodecanoate was added and homogenized for 0.5 hours. The mixture was heated to 130°C and 93.00 g (0.0694 mol) of polyester 1 was added. The mixture was held at 130°C for 3 hours, and then the reaction mixture was cooled to room temperature. The acid value was 32.8 mg KOH / g. This corresponds to 86.3% of the polyester segment bonded to the polyamine core via ionic bonds.

[0071] Example 4 7.0 g (0.0007 mol) of PEI 1 was added to a 4-neck flask and heated to 110°C. 0.63 g (0.0028 mol) of glycidyl neodecanoate was added and homogenized for 0.5 hours. The mixture was heated to 130°C and 93.00 g (0.0694 mol) of polyester 1 was added. The mixture was held at 130°C for 3 hours, and then the reaction mixture was cooled to room temperature. The acid value was 33.0 mg KOH / g. This corresponds to 85.3% of the polyester segment bonded to the polyamine core via ionic bonds.

[0072] Example 5 7.0 g (0.0007 mol) of PEI 1 was added to a 4-neck flask and heated to 110°C. 0.93 g (0.0055 mol) of ethylhexyl glycidyl ether was added and homogenized for 0.5 hours. The mixture was heated to 130°C and 93.00 g (0.0694 mol) of polyester 1 was added. The mixture was held at 130°C for 3 hours, and then the reaction mixture was cooled to room temperature. The acid value was 33.0 mg KOH / g. This corresponds to 85.5% of the polyester segment bonded to the polyamine core via ionic bonds.

[0073] Example 6 7.0 g (0.0007 mol) of PEI 1 was added to a 4-neck flask and heated to 110°C. 0.91 g (0.0055 mol) of cresylglycidyl ether was added and homogenized for 0.5 hours. The mixture was heated to 130°C and 93.00 g (0.0694 mol) of polyester 1 was added. The mixture was held at 130°C for 3 hours, and then the reaction mixture was cooled to room temperature. The acid value was 33.0 mg KOH / g. This corresponds to 85.7% of the polyester segment bonded to the polyamine core via ionic bonds.

[0074] Example 7 12.2 g (0.0925 mol) of PEI 3 was added to a 4-neck flask and heated to 110°C. 16.67 g (0.0731 mol) of glycidyl neodecanoate was added and homogenized for 0.5 hours. 34.81 g (0.0174 mol) of polyester 2 and 11.6 g (0.0058 mol) of polyester 3 were added. The mixture was heated to 130°C and held at this temperature for 3 hours, after which the reaction mixture was cooled to room temperature.

[0075] Comparative Example 3 12.2 g (0.0925 mol) of PEI 3 was added to a four-neck flask and heated to 80°C. 34.81 g (0.0174 mol) of polyester 2 and 11.6 g (0.0058 mol) of polyester 3 were added. The mixture was heated to 130°C and held at this temperature for 3 hours, after which the reaction mixture was cooled to room temperature. The acid value was 18.6 mg KOH / g, which corresponds to 84.1% of the polyester segment ionically bonded to the polyamine core.

[0076] Example 8 12.55 g (0.00125 mol) of PEI 1 was added to a 4-neck flask and heated to 110°C. 16.13 g (0.0708 mol) of glycidyl neodecanoate was added and homogenized for 0.5 hours. 33.69 g (0.0168 mol) of polyester 2 and 11.22 g (0.0056 mol) of polyester 3 were added. The mixture was heated to 130°C and held at this temperature for 3 hours, after which the reaction mixture was cooled to room temperature.

[0077] Comparative Example 4 12.55 g (0.00125 mol) of PEI 1 was added to a 4-neck flask and heated to 80°C. 33.69 g (0.0171 mol) of polyester 2 and 11.22 g (0.0056 mol) of polyester 3 were added. The mixture was heated to 130°C and held at this temperature for 3 hours, after which the reaction mixture was cooled to room temperature.

[0078] Application Test 0.3 g of dispersant was homogenized in 16.7 g of N-methylpyrrolidone in a 250 ml polypropylene cup. Next, 3 g of conductive carbon black (IMERYS C-Nergy SUPER C 65) and 40 g of glass beads (0.75 mm) were added. Dispersion was performed using a Hauschild SpeedMixer DAC 400 at 1400 rpm for 9 minutes, after which the glass beads were sieved off. Finally, the slurry was evaluated by measuring its viscosity in an Anton Paar MCR 102 at 23 °C using a cone / plate geometry (25 mm diameter, 1° angle cone).

[0079] The viscosity measurement results are summarized in the table below.

[0080] [Table 1]

[0081] The tests conducted in Comparative Examples 1 and 2 produced slurries with such high viscosity that it was impossible to sieve the glass beads. Therefore, these comparative dispersants made the viscosity of the slurry unacceptably high. Comparative Example 3 similarly produced an unacceptably high viscosity slurry. The slurries prepared in the examples of the present invention all have significantly lower viscosity than those in the comparative examples. This conclusion is valid for a variety of shear rates.

[0082] 0.3 g of dispersant was homogenized in 16.7 g of NMP in a 250 ml polypropylene cup. Next, 3 g of conductive carbon black (Denka Black Li 400) and 40 g of glass beads (0.75 mm) were added. Dispersion was performed using a Hauschild SpeedMixer DAC 400 at 1400 rpm for 9 minutes, after which the glass beads were sieved off. Finally, the slurry was evaluated by measuring its viscosity in an Anton Paar MCR 102 at 23°C using a cone / plate geometry (25 mm diameter, 1° angle cone).

[0083] The viscosity measurement results are summarized in the table below.

[0084] [Table 2]

[0085] The test conducted in Comparative Example 1 produced a slurry with such high viscosity that it was impossible to sieve the glass beads. Therefore, this comparative dispersant made the viscosity of the slurry unacceptably high. Comparative Example 4 similarly produced a slurry with unacceptably high viscosity. The slurries prepared in the examples of the present invention all have significantly lower viscosity than the comparative examples. This conclusion is valid for a variety of shear rates.

Claims

1. (a) A polymer, (i) A polyamine core comprising multiple amine groups and having the structure of formula (I), 【Chemistry 1】 In the formula, R １ H or a part of the polyamine core, R ２ H or an organic group, R ３ is H or an organic group, however R ２ and R ３ At least one of them is H, (ii) A plurality of polyester segments bonded to the polyamine core via ionic bonds, Polymers having, and (b) Electrically conductive carbon-based material, including, A composition, The weight ratio of the polymer (a) to the electrically conductive carbon-based material (b) in the composition of the present invention is in the range of 70:100 to 3:

100. composition.

2. The composition according to claim 1, wherein the polyamine core is polyethyleneimine.

3. The composition according to claim 1 or 2, wherein the weight-average molecular weight of the polyamine core is in the range of 300 to 25,000 g / mol.

4. R ２ and R ３ The composition according to any one of claims 1 to 3, wherein the group is independently selected from a hydrocarbyl group, an organic group containing an ether group, and an organic group containing an ester group.

5. The composition according to any one of claims 1 to 4, wherein the polymer further comprises a polyester segment bonded to the polyamine core via an amide group.

6. The composition according to claim 5, wherein 10 to 40% of the polyester segment is bonded to the polyamine core via amide groups, and 90 to 60% of the polyester segment is bonded to the polyamine core via ionic bonds.

7. where the polyester segment contains repeating units of the formula -[-O-(CH ２ ), ｎ -C(=O)]-, and n is an integer in the range of 3 to 6, the composition according to any one of claims 1 to 6.

8. The composition according to any one of claims 1 to 7, wherein the carbon-based material comprises at least one of carbon black, carbon nanotubes, graphite, carbon fibers, graphene, and fullerene.

9. The composition according to any one of claims 1 to 8, wherein the weight ratio of the polymer (a) to the electrically conductive carbon-based material (b) in the composition of the present invention is in the range of 50:100 to 5:

100.

10. The composition according to any one of claims 1 to 9, further comprising a cathode active material for rechargeable batteries.

11. The composition according to claim 10, wherein the cathode active material comprises at least one of lithium nickel cobalt aluminum oxide and lithium nickel manganese cobalt oxide.

12. The composition according to any one of claims 1 to 11, further comprising at least one organic solvent in an amount of 10 to 90% by weight, calculated based on the total weight of the composition.

13. The composition according to any one of claims 1 to 12, further comprising a polymer binder different from the polymer contained in the composition according to any one of claims 1 to 12.

14. Use of the composition according to any one of claims 1 to 13 for manufacturing electrodes for rechargeable batteries.

15. A process for manufacturing a rechargeable electric battery electrode, comprising manufacturing a battery electrode using the composition described in any one of claims 1 to 13.

16. An electrostatic battery electrode comprising the composition according to any one of claims 1 to 13.

17. A rechargeable electric battery comprising the electrode described in claim 16.

18. Uses of polymers having the following properties for the manufacture of compositions for producing electrodes for rechargeable batteries: (i) A polyamine core comprising multiple amine groups and having the structure of formula (I), 【Chemistry 2】 In the formula, R １ H is part of the polyamine core, and R ２ is H or an organic group, R ３ is H or an organic group, however R ２ and R ３ At least one of them is H, (ii) A plurality of polyester segments bonded to the polyamine core via ionic bonds.

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