Electrode components

Abstract

This application illustrates and describes a composition suitable for electrochemical devices. This composition comprises an organically functionalized substance having a nitrogen functional group. In the embodiment, the nitrogen functional group is a ureid functional group. This composition can be used as an electrode material in electrochemical batteries, such as lithium batteries.

Description

[Technical Field]

[0001] The present invention relates to compositions for electrodes. In particular, the present invention relates to compositions comprising ureido-functional compounds as additives, and compositions suitable for use in forming electrodes. [Background technology]

[0002] As the use of batteries increases in various applications, such as electric vehicles, electronic consumables, and other uses, the demand for the development and improvement of energy generation and energy storage devices continues to grow. Manufacturers aim to improve battery performance, such as high capacity, fast charging, long storage life, and other characteristics. These performance characteristics are directly influenced by the electrochemical reactions occurring inside the battery.

[0003] Graphite is a common material for negative electrodes. Graphite has an irreversible capacity of 372 mAh / g. This limited capacity prevents its application to next-generation high-capacity batteries intended for long-term use on a single charge.

[0004] Lithium batteries are used with great interest in industry. One method to improve the capacity of lithium batteries is to dope composite materials with high-capacity materials and graphite, or to develop such composite materials. Possible negative electrode materials include oxides, carbides, and / or nitrides of tin, germanium, and / or silicon. Silicon and silicon-based anode materials are of particular interest due to their high specific capacity. These materials are also generally readily available in large quantities. Silicon can exhibit capacities up to 3700 mAh / g. Silicon monoxide can yield capacities of around 1850 mAh / g.

[0005] However, silicon materials exhibit high expansion properties during lithiation. Silicon can expand up to 400% in volume compared to its initial dimensions. This causes electrode cracking and leads to a decrease in capacity. Silicon also undergoes a high degree of granulation during its reaction with lithium, resulting in an irreversible increase in capacity. This also causes a decrease (or decay) in capacity as the battery undergoes charging cycles. [Overview of the project]

[0006] The following is a summary of the disclosure, providing a basic understanding of several embodiments. This summary is not intended to identify any important or essential elements of the embodiments or claims, nor does it impose any limitations. Furthermore, this summary may present a simplified overview of several embodiments, which may be described in detail in other parts of the disclosure.

[0007] Provided is a composition suitable for use in electrodes. This composition contains a nitrogen-containing organosilicon material as an additive. In embodiments, the nitrogen-containing organosilicon material is a ureid-functional organosilicon material. The ureid-functional organosilicon material has been found to result in an electrode material with excellent capacity retention over a large number of charge cycles (i.e., charge / discharge cycles). This is observed at both constant current density and variable charge / discharge rates. Materials comprising the ureid-functional organosilicon material also exhibit excellent capacity recovery after reversing the current density. This material also exhibits low impedance over charge / discharge cycles.

[0008] In one embodiment, the provided composition is: (a) Polymer resin; (b) Compounds represented by formula (I); [ka] R in the formula 1 ', R 2 ', R3 ', R 4 ' and R 5 ' and R 6 ' are each independently selected from R 4 , OR 5 , and a ureido functional group, wherein R 4 is each independently selected from monovalent groups selected from the group consisting of linear alkyl having 1 to 12 carbon atoms, branched alkyl having 3 to 12 carbon atoms, cyclic alkyl having 5 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, aryl groups having 6 to 20 carbon atoms, and aralkyl having 7 to 20 carbon atoms; R 5 is each independently selected from monovalent groups selected from the group consisting of linear alkyl having 1 to 12 carbon atoms, branched alkyl having 3 to 12 carbon atoms, cyclic alkyl having 5 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, aryl groups having 6 to 20 carbon atoms, and aralkyl having 7 to 20 carbon atoms; a' or b' is 0 to 500, provided that at least one of a' and b' is greater than 0; and R 1 ', R 2 ', R 3 ', R 4 ', R 5 ' and / or R 6 ' is at least one ureido functional group; wherein the ureido functional group has the formula: [Chemical Formula] , wherein R 1 and R 2 are each independently selected from the group consisting of hydrogen and monovalent organic groups having 1 to 20 carbon atoms; R 3is a divalent linear alkylene group having 1 to 20 carbon atoms, or a divalent branched alkylene group having 3 to 20 carbon atoms, each optionally containing one or more heteroatoms in the chain; X is selected from the group consisting of substituted or unsubstituted aromatic groups having 6 to 20 carbon atoms and heterocyclic groups containing 1 to 20 heteroatoms, where the aromatic group and / or heterocyclic group are optionally substituted with an alkyl group having 1 to 12 carbon atoms and optionally containing heteroatoms and ureid functional groups selected from the group consisting of O, N, and / or S; and Z is oxygen; (c) Electrode active material; and (d) optionally contains a binder.

[0009] In one embodiment, the polymer resin is selected from one or more of the group consisting of polyethylene, polypropylene, polyethylene terephthalate, polymethyl methacrylate, aromatic polyamide, chitosan, alginic acid, polyacrylic acid, polyimide, cellulose, carboxymethylcellulose, nitrocellulose; styrene-butadiene rubber (SBR), isoprene rubber, butadiene rubber, fluoroelastomer, acrylonitrile-butadiene rubber (NBR), ethylene propylene rubber; styrene-butadiene styrene block copolymer and its hydrogenation products; EPDM (ethylene propylene dienterpolymer), styrene-ethylene butadiene styrene copolymer, styrene-isoprene styrene block copolymer and its hydrogenation products; syndiotactic-1,2-polybutadiene, polyvinyl acetate, ethylene vinyl acetate copolymer, and propylene-α-olefin copolymer; polyvinylidene fluoride, polytetrafluoroethylene, vinylidene fluoride copolymer, and tetrafluoroethylene-ethylene copolymer; and polymers containing alkali metal ions.

[0010] In one embodiment according to any one of the preceding embodiments, the optional binder is selected from one or more selected from the group consisting of carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, oxidized starch, monostarch phosphate, casein, polyvinylpyrrolidone, and salts thereof.

[0011] In one embodiment according to any one of the preceding embodiments, the electrode active material is selected from the group consisting of one or more of an intercalation agent and a conductive agent. In one embodiment, the intercalation agent is graphite, lithium nickel manganese cobalt oxide (LiNMC), Si, SiB₄, SiB₆, Mg₂Si, Ni₂Si, TiSi₂, MoSi₂, CoSi₂, NiSi₂, CaSi₂, CrSi₂, Cu₆Si, FeSi₂, MnSi₂, NbSi₂, TaSi₂, VSi₂, WSi₂, ZnSi₂, SiC, Si₃N₄, Si₂N₂O, SiO v (0 < v ≤ 2), LiSiO, Sn, SnSiO₃, LiSnO, and Mg₂Sn, SnO w (0 < w ≤ 2).

[0012] In one embodiment, the conductive agent is a carbonaceous conductive agent selected from the group consisting of graphite including natural graphite and artificial graphite, carbon black including acetylene black, Ketjen black, channel black, furnace black, lamp black and thermal black, amorphous carbon including needle coke, carbon nanotubes, fullerenes, and vapor grown carbon fiber (VGCF).

[0013] In one embodiment according to any one of the preceding embodiments, the condition is a' > 0 and b' = 0, and the compound represented by formula (I) is polysilane.

[0014] In one embodiment according to any one of the preceding embodiments, the compound of formula (I) is of the formula:

Chemical Formula

[0015] In one embodiment according to any of the above embodiments, the condition is b'>0, a'=0, and the compound represented by formula (I) is a polysiloxane.

[0016] In one embodiment according to any of the preceding embodiments, the compound represented by formula (I) is a ureido-functional organosilicon.

[0017] In one embodiment according to any of the preceding embodiments, the ureido-functional organosilicon is given by formula: [ka] It is a compound of the formula, and in the formula R 1 and R 2 Each of these is an independent monovalent organic group having either hydrogen or 1 to 20 carbon atoms; R 3 These are divalent linear alkylene groups having 1 to 20 carbon atoms, or divalent branched alkylene groups having 3 to 20 carbon atoms, each optionally containing one or more heteroatoms in the chain; R 4 This is independently a monovalent group selected from the group consisting of linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, cyclic alkyl groups having 5 to 12 carbon atoms, alkenyl groups having 2 to 12 carbon atoms, aryl groups having 6 to 20 carbon atoms, and aralkyl groups having 7 to 20 carbon atoms; R 5 These are independently selected from the group consisting of linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, cyclic alkyl groups having 5 to 12 carbon atoms, alkenyl groups having 2 to 12 carbon atoms, aryl groups having 6 to 20 carbon atoms, and aralkyl groups having 7 to 20 carbon atoms; X is an aromatic group having 6 to 20 carbon atoms or a heterocyclic group containing up to 20 heteroatoms, where the aromatic group or heterocyclic group is optionally substituted with an alkyl group having 1 to 12 carbon atoms, optionally containing a heteroatom selected from the group consisting of O, N, and / or S, and a ureid functional group: Z is oxygen; and a is an integer that has a value of 1, 2, or 3.

[0018] In one embodiment according to any of the preceding embodiments, the compound of formula (I) is a polysiloxane represented by the following formula: M 1 a M 2 b D 1 c D 2 d T 1 e T2 f Q g In the formula: M 1 is (R 16 )(R 17 )(R 18 )SiO 1 / 2 M 2 is (R 19 (R 20 (R 21 )SiO 1 / 2 D 1 is (R 22 (R 23 )SiO 2 / 2 D 2 is (R 24 (R 25 )SiO 2 / 2 T 1 is (R 26 )SiO 3 / 2 T 2 is (R 27 )SiO 3 / 2 Q is SiO 4 / 2 R 16 , R 17 , R 18 , R 22 , R 23 , and R 26 are independently selected from the group consisting of R 4 and OR 5 ; R 19 , R 20 , R 21 , R 24 , R 25 , and R 27 are independently selected from the group consisting of R 4 , OR 5 and a ureido functional group, with the proviso that at least one of R 19 , R 20 , R 21 , R 24 , R 25 , and R 27 is a ureido functional group; wherein R 4The group is independently selected from the group consisting of monovalent groups selected from linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, cyclic alkyl groups having 5 to 12 carbon atoms, alkenyl groups having 2 to 12 carbon atoms, aryl groups having 6 to 20 carbon atoms, and aralkyl groups having 7 to 20 carbon atoms; R 5 These are independently selected from the group consisting of linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, cyclic alkyl groups having 5 to 12 carbon atoms, alkenyl groups having 2 to 12 carbon atoms, aryl groups having 6 to 20 carbon atoms, and aralkyl groups having 7 to 20 carbon atoms; b, d, and f are independent integers greater than 0; and a, c, e, and g are each independent integers greater than 0.

[0019] In one embodiment according to any of the preceding embodiments, X is a six-membered ring containing up to 5 nitrogen atoms.

[0020] In one embodiment according to any of the preceding embodiments, X is a six-membered ring containing one or two nitrogen atoms.

[0021] In one embodiment according to any of the above embodiments, X is [ka] Selected from, here R 11 This is selected from the group consisting of a monovalent organic group having hydrogen and 1 to 12 carbon atoms.

[0022] In one embodiment according to any of the above embodiments, X is [ka] Here, J1, J2, and J3 are independently substituted or unsubstituted C or N atoms, and the dashed lines between J1, J2, and J3 indicate optional double bonds between J1 and J2 or between J2 and J3.

[0023] In one embodiment according to any of the above embodiments, the substituents in X are represented by the following formula: [ka] R in the formula 6 and R 7 Each of these is an independent monovalent organic group having either hydrogen or 1 to 20 carbon atoms; R 8 These are divalent linear alkylene groups having 1 to 20 carbon atoms, or divalent branched alkylene groups having 3 to 20 carbon atoms, each optionally containing one or more heteroatoms in the chain; R 9 Each is independently selected from the group consisting of monovalent groups selected from linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, cyclic alkyl groups having 5 to 12 carbon atoms, alkenyl groups having 2 to 12 carbon atoms, aryl groups having 6 to 20 carbon atoms, and aralkyl groups having 7 to 20 carbon atoms; R 10 is independently selected from the group consisting of linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, cyclic alkyl groups having 5 to 12 carbon atoms, alkenyl groups having 2 to 12 carbon atoms, aryl groups having 6 to 20 carbon atoms, and aralkyl groups having 7 to 20 carbon atoms; and here b is an integer that has a value of 1, 2, or 3.

[0024] In one embodiment according to any of the preceding embodiments, the ureid of the functionalized organosilicon is represented by the following formula: [ka]

[0025] In one embodiment according to any of the preceding embodiments, the compound represented by formula (I) is present in an amount of about 0.1 to 10% by weight based on the total weight of the composition.

[0026] In one embodiment according to any of the preceding embodiments, the compound of formula (I) is present in amounts of about 0.01% to about 90% by weight, about 0.05% to about 80% by weight, about 0.1% to about 75% by weight, about 0.2% to about 60% by weight, about 0.5% to about 50% by weight, about 1% to about 25% by weight, or about 5% to about 10% by weight, based on the total weight of the composition; preferably, it is present in amounts of 1 to 10% by weight, 10 to 50% by weight, or 50 to 90% by weight, based on the total weight of the composition.

[0027] In one embodiment according to any of the preceding embodiments, the composition is a solvent-free composition.

[0028] In one embodiment, the provided energy storage device comprises: (a) at least one electrode; and (b) an electrolyte, wherein the at least one electrode comprises any one of the compositions of the preceding embodiments.

[0029] In one embodiment, the device has a specific capacitance determined by cycle stability testing after at least 500 electrochemical cycles that is at least 20% of the specific capacitance after the first cycle. In one embodiment according to any of the preceding embodiments, the device has a specific capacitance determined by cycle stability testing after at least 500 electrochemical cycles that is at least 40% of the specific capacitance after the first cycle. In one embodiment according to any of the preceding embodiments, the device has a specific capacitance determined by cycle stability testing after at least 500 electrochemical cycles that is at least 60% of the specific capacitance after the first cycle.

[0030] In one embodiment according to any of the preceding embodiments, the device is a rechargeable battery.

[0031] In one embodiment according to any of the above embodiments, the secondary battery is a lithium-ion battery.

[0032] In yet another embodiment, an energy storage device is provided, comprising: at least one electrode and an electrolyte, wherein the at least one electrode comprises: (a) a polymer resin; (b) a capacity retainer; (c) an electrode active material; and (d) optionally a binder, wherein the capacity retainer maintains the specific capacity of the electrode after 500 electrochemical cycles in the range of at least 20-80% of the specific capacity after the first cycle.

[0033] In one embodiment, the volume retainer is represented by the following formula: [ka] R in the formula 1 ', R 2 ', R 3 ', R 4 ', R 5 ', and R 6 Each of the following is independent of R 4 , OR 5 , or a ureido functional group, where R 4 These are independently linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, cyclic alkyl groups having 5 to 12 carbon atoms, alkenyl groups having 2 to 12 carbon atoms, aryl groups having 6 to 20 carbon atoms, or aralkyl groups having 7 to 20 carbon atoms; R 5 These are independently linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, cyclic alkyl groups having 5 to 12 carbon atoms, alkenyl groups having 2 to 12 carbon atoms, aryl groups having 6 to 20 carbon atoms, or aralkyl groups having 7 to 20 carbon atoms; a' or b' are integers whose values ​​are between 0 and 500, provided that at least one of a' or b' is > 0; and R 1 ', R 2 ', R 3 ', R 4 ', R 5 ', and / or R 6 At least one of the ' groups is a ureido functional group.

[0034] In one embodiment, the ureido functional group is of the formula: [ka] It is expressed by, where R 1 and R 2 Each is independently selected from the group consisting of a hydrogen atom and a monovalent organic group having 1 to 20 carbon atoms; R 3 These are divalent linear alkylene groups having 1 to 20 carbon atoms, or divalent branched alkylene groups having 3 to 20 carbon atoms, each optionally containing one or more heteroatoms in the chain; X is selected from the group consisting of substituted or unsubstituted aromatic groups having 6 to 20 carbon atoms and heterocyclic groups containing 1 to 20 heteroatoms, where the aromatic group and / or heterocyclic group is optionally substituted with an alkyl group having 1 to 12 carbon atoms and optionally containing a heteroatom and a ureid functional group, which are optionally selected from the group consisting of O, N, and / or S: and Z is oxygen.

[0035] In a further embodiment, an electrode comprising a composition according to any one of the preceding embodiments is provided.

[0036] In yet another embodiment, the provided is an electrochemical cell comprising a negative electrode and a positive electrode, wherein the negative electrode, the positive electrode, or both the negative and positive electrodes comprise the composition of claim 1-21.

[0037] In one embodiment, the electrochemical battery further includes a separator.

[0038] In one embodiment according to any of the preceding embodiments, the electrochemical battery is a lithium-ion battery.

[0039] In another embodiment, the provided energy storage device comprises: (a) at least one electrode; and (b) an electrolyte, wherein at least one electrode comprises the present composition.

[0040] In another aspect, the provided electrode comprises the composition shown and described herein.

[0041] In yet another embodiment, the provided electrochemical cell comprises a negative electrode and a positive electrode, wherein the negative electrode, the positive electrode, or both the negative and positive electrodes contain the composition shown and described herein.

[0042] In yet another embodiment, an energy storage device is provided, comprising: at least one electrode and an electrolyte, wherein the at least one electrode comprises: (a) a polymer resin; (b) a capacity retainer; (c) an electrode active material; and (d) optionally a binder, wherein the capacity retainer maintains the specific capacity of the electrode in the range of at least 20-80% of the specific capacity after the first cycle after 500 electrochemical cycles.

[0043] The following description of the drawings discloses various exemplary embodiments. Some improvements and novel embodiments may be explicitly identified, while others may be apparent from the detailed description and drawings. [Brief explanation of the drawing]

[0044] Figure 1 shows a cyclic voltammogram of a battery using a composition containing a ureid-functional organosilicon material;

[0045] Figure 2 shows the cyclic voltammogram of a battery using a control binder that does not contain ureid-functional organosilicon materials; and

[0046] Figure 3 shows the galvanostatic charge-discharge curves (GCD) at various cycle counts. [Modes for carrying out the invention]

[0047] Referencing the following exemplary embodiments, examples are illustrated in the accompanying drawings. As will be understood, other embodiments may also be used, and structural and functional modifications may be made. Furthermore, features of various embodiments may be combined or modified. Thus, the following description is presented merely as an example and does not in any way limit the various alternatives or modifications that may be made to the exemplary embodiments. In this disclosure, several specific details will lead to a complete understanding of the disclosed subject matter. It should be understood that embodiments of this disclosure may be implemented in other embodiments that do not necessarily include all aspects described in this application or elsewhere.

[0048] As used in this application, the terms “example” and “illustration” mean examples or illustrations. The terms “example” and “illustration” do not indicate essential or preferred embodiments or forms. The term “or” is intended to be inclusive, not exclusive, unless the context suggests otherwise. For example, the statement “A uses B or C” includes any inclusive substitution (e.g., A uses B; A uses C; or A uses both B and C). Separately, the articles “one” and “a” are generally intended to mean “one or more,” unless the context suggests otherwise.

[0049] Provided in this application is a composition suitable for use in electrodes, wherein the composition comprises a polymer resin, a compound, an electrode active material, and optionally a binder. The compound is a ureido-functional organosilicon material.

[0050] In one embodiment, the ureido-functional organosilicon material comprises a ureido-functional silane. In another embodiment, the ureido-functional organosilicon material comprises a ureido-functional siloxane. The ureido-functional organosilicon material is suitable for use as a binding additive in electrode compositions that may be used to constitute electrochemical cells such as batteries. The ureido-functional organosilicon material can be mixed with polymer resins, electrode active materials, and binding additives to form compositions useful for positive or negative electrodes.

[0051] This composition contains a ureido-functional organosilicon material as an additive. The ureido-functional organosilicon may be represented by the compound of formula (I): [ka] R in the formula 1 ', R 2 ', R 3 ', R 4 ', R 5 ', and R 6 Each of these is independent of R 4 , OR 5 Selected from the group consisting of , and ureido functional groups, where R 4 R is independently selected from a monovalent group selected from the group consisting of linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, cyclic alkyl groups having 5 to 12 carbon atoms, alkenyl groups having 2 to 12 carbon atoms, aryl groups having 6 to 20 carbon atoms, and aralkyl groups having 7 to 20 carbon atoms; 5 It is independently selected from a monovalent group selected from the group consisting of a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a cyclic alkyl group having 5 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms; a' or b' is between 0 and 500, provided that at least one of these a' or b' is >0; and R 1 'from R 6At least one of the ' is a ureid functional group. As can be understood, if a' is greater than 0, then b' is 0, and if b' is greater than 0, then a' is 0.

[0052] The ureido functional group is given by the formula: [ka] It is and in the formula R 1 and R 2 Each is independently selected from a monovalent organic group having hydrogen or 1 to 20 carbon atoms; R 3 This is a divalent linear alkylene group having 1 to 20 carbon atoms, or a divalent branched alkylene group having 3 to 20 carbon atoms, each of which can optionally contain one or more heteroatoms in the chain; X is selected from the group consisting of aromatic groups having 6 to 20 carbon atoms and heterocyclic groups containing 5 to 20 heteroatoms, where the aromatic group and / or heterocyclic group is optionally substituted with an alkyl group having 1 to 12 carbon atoms and optionally containing a heteroatom or ureid functional group selected from the group consisting of O, N, and / or S: and Z is oxygen.

[0053] In one embodiment, the ureido-functional organosilicon material is a silane (b' = 0) of the following formula: [ka] R in the formula 1’ , R 3’ , R 5’ , and R 6’ Each is independently R 4 , OR 5 Selected from , and ureido functional groups, where R 4The group is independently selected from a monovalent group chosen from a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a cyclic alkyl group having 5 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms; R 5 The group is independently selected from a monovalent group chosen from a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a cyclic alkyl group having 5 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms; a' is 1-500; and R 1’ , R 3’ , R 5’ , and R 6’ At least one of these is selected from the ureido functional group.

[0054] In one embodiment, R 6’ is a ureido functional group, and R 1’ , R 3’ , and R 5’ Each is independently R 4 and OR 5 Selected from .

[0055] In one embodiment, the ureido-functional organosilicon material is a silane selected from the following compounds: [ka] R in the formula 1 and R 2 Each is independently selected from a monovalent organic group having hydrogen or 1 to 20 carbon atoms; R 3 This is a divalent linear alkylene group having 1 to 20 carbon atoms, or a divalent branched alkylene group having 3 to 20 carbon atoms, each of which can optionally contain one or more heteroatoms in the chain; R 4 The group is independently selected from a monovalent group chosen from a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a cyclic alkyl group having 5 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms; R 5 The group is independently selected from a monovalent group chosen from a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a cyclic alkyl group having 5 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms; X is selected from the group consisting of aromatic groups having 6 to 20 carbon atoms and heterocyclic groups containing up to 20 heteroatoms, where the aromatic group and / or heterocyclic group is optionally substituted with an alkyl group having 1 to 12 carbon atoms and optionally containing a heteroatom or ureid functional group selected from the group consisting of O, N, and / or S: Z is oxygen; and a is 1, 2, or 3. n ranges from 1 to 500. R 1 and R 2 Each is independently selected from hydrogen and a monovalent group having 1 to 20 carbon atoms, 2 to 15 carbon atoms, 4 to 12 carbon atoms, or 6 to 10 carbon atoms. Suitable examples of monovalent organic groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and others. In one embodiment, R 1 and R 2 Each is independently selected from hydrogen and a monovalent group having 1 to 4 carbon atoms. In one embodiment, R 1 and R 2 Each of these is hydrogen.

[0056] In one embodiment, R 3This is selected from divalent linear alkylene groups containing 1 to 12 carbon atoms, 1 to 8 carbon atoms, and 1 to 4 carbon atoms, or 3 carbon atoms, such as (-CH2-)3.

[0057] In one embodiment, R 4 R is independently a monovalent group selected from linear alkyl groups containing 1 to 8 carbon atoms, 1 to 4 carbon atoms, or 1 to 2 carbon atoms, or branched alkyl groups containing 3 to 8 carbon atoms, 4 to 6 carbon atoms, or 3 to 4 carbon atoms. 4 Examples of groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, and others; cycloalkyl groups containing 6 carbon atoms; alkenyl groups containing 2 to 8 carbon atoms, preferably 2 to 4 carbon atoms; aryl groups, such as phenyl; aralkyl groups containing 7 to 10 carbon atoms, preferably 7 to 9 carbon atoms; linear alkyl groups containing 2 to 8 carbon atoms and a hydroxyl group, preferably 2 to 4 carbon atoms and a hydroxyl group; or branched alkyl groups containing 3 or 4 carbon atoms and a hydroxyl group.

[0058] R 5 The group is independently a monovalent group selected from a linear alkyl group containing 1 to 8 carbon atoms, 1 to 4 carbon atoms, or 1 to 2 carbon atoms, a branched alkyl group containing 3 to 8 carbon atoms, 3 to 6 carbon atoms, or 3 to 4 carbon atoms, a cycloalkyl group containing 6 carbon atoms, an alkenyl group containing 2 to 8 carbon atoms, or 2 to 6 carbon atoms, an aryl group such as phenyl, or an aralkyl group containing 7 to 10 carbon atoms, or 7 to 9 carbon atoms.

[0059] In one embodiment, X is selected from an aromatic group containing six carbon atoms, such as phenyl, or a heterocyclic group containing six atoms and up to five heteroatoms. X can be substituted or unsubstituted. X may be substituted, for example, with an alkyl group having 1 to 12 carbon atoms, 2 to 10 carbon atoms, or 4 to 6 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a ureido functional group, or a heteroatom selected from N or O. In one embodiment, X is a substituted or unsubstituted phenyl group. In one embodiment, X is a six-membered heterocyclic group containing 1 to 5 heteroatoms selected from nitrogen, 3 heteroatoms selected from nitrogen, or 1 or 2 heteroatoms selected from nitrogen.

[0060] In one embodiment, X is selected from the following equation: [ka] Here, J1, J2, and J3 are independently substituted or unsubstituted carbon or nitrogen atoms, and the dashed lines between J1, J2, and J3 indicate optional double bonds between J1 and J2 or between J2 and J3. If any of J1, J2, or J3 is a substituted nitrogen atom, that atom is not involved in the double bond.

[0061] Some non-specific examples of X include: [ka] This includes R 11 This is selected from a monovalent organic group having hydrogen and 1 to 12 carbon atoms.

[0062] X can be substituted with an alkyl group having 1 to 12 carbon atoms, 2 to 10 carbon atoms, or 4 to 6 carbon atoms, or with a ureid functional group. This alkyl group optionally contains a heteroatom selected from O, N, and / or S. In one embodiment, the X group is a ureid functional group of the following formula: [ka]

[0063] It is replaced by R here 6 and R 7 Each is independently selected from a monovalent organic group having hydrogen or 1 to 20 carbon atoms;

[0064] R 8 This is a divalent linear alkylene group having 1 to 20 carbon atoms, or a divalent branched alkylene group having 3 to 20 carbon atoms, each of which can optionally contain one or more heteroatoms in the chain;

[0065] R 9 Each is independently selected from monovalent groups chosen from linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, cyclic alkyl groups having 5 to 12 carbon atoms, alkenyl groups having 2 to 12 carbon atoms, aryl groups having 6 to 20 carbon atoms, and aralkyl groups having 7 to 20 carbon atoms;

[0066] R 10 Each is independently selected from monovalent groups chosen from linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, cyclic alkyl groups having 5 to 12 carbon atoms, alkenyl groups having 2 to 12 carbon atoms, aryl groups having 6 to 20 carbon atoms, and aralkyl groups having 7 to 20 carbon atoms; and

[0067] b is 1, 2, or 3.

[0068] R 6 and R 7Each is independently selected from a monovalent group having hydrogen, 1 to 20 carbon atoms, 2 to 15 carbon atoms, 4 to 12 carbon atoms, or 6 to 10 carbon atoms. Suitable examples of monovalent organic groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and others. In one embodiment, R 6 and R 7 R is independently selected from hydrogen and a monovalent group having 1 to 4 carbon atoms. In one embodiment, R 6 and R 7 Each of them is hydrogen.

[0069] In one embodiment, R 8 This is selected from divalent linear alkylene groups containing 1 to 12 carbon atoms, 1 to 8 carbon atoms, 1 to 4 carbon atoms, or 3 carbon atoms, such as (-CH2-)3.

[0070] In one embodiment, R 9 Each of these is independently a monovalent group selected from a linear alkyl group containing 1 to 8 carbon atoms, 1 to 4 carbon atoms, or 1 to 2 carbon atoms, or a branched alkyl group containing 3 to 8 carbon atoms, or 3 to 4 carbon atoms. 9 Suitable groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl and others; cycloalkyl groups containing 6 carbon atoms; alkenyl groups containing 2 to 8 carbon atoms, preferably 2 to 4 carbon atoms; aryl groups, such as phenyl; or aralkyl groups containing 7 to 10 carbon atoms, preferably 7 to 9 carbon atoms; linear alkyl groups containing 2 to 8 carbon atoms and a hydroxyl group, preferably 2 to 4 carbon atoms and a hydroxyl group; or branched alkyl groups containing 3 or 4 carbon atoms and a hydroxyl group.

[0071] R 10The group is independently a monovalent group selected from a linear alkyl group containing 1 to 8 carbon atoms, 1 to 4 carbon atoms, or 1 to 2 carbon atoms, a branched alkyl group containing 3 to 8 carbon atoms, 3 to 6 carbon atoms, or 3 to 4 carbon atoms, a cycloalkyl group containing 6 carbon atoms, an alkenyl group containing 2 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, an aryl group, such as phenyl, or an aralkyl group containing 7 to 10 carbon atoms, or 7 to 9 carbon atoms.

[0072] In one embodiment of formula (I), R 1 and R 2 H and Z are O and R respectively. 3 R is a divalent linear alkylene group containing 2 to 6 carbon atoms, the subscript a is 3, and R 4 Each of these is a linear alkyl group containing 1 to 3 carbon atoms.

[0073] In another embodiment of formula (I), X is a phenyl group, R 1 and R 2 H and Z are O and R respectively. 3 R is a divalent linear alkylene group containing 2 to 6 carbon atoms, the subscript a is 3, and R 4 Each of these is a linear alkyl group containing 1 to 3 carbon atoms.

[0074] In another embodiment of formula (I), X is a heterocyclic group containing 1 or 2 N atoms, R 1 and R 2 H and Z are O and R respectively. 3 R is a divalent linear alkylene group containing 2 to 6 carbon atoms, the subscript a is 3, and R 4 Each of these is a linear alkyl group containing 1 to 3 carbon atoms.

[0075] In another embodiment of formula (I), X is a heterocyclic group containing 2 N atoms, and the ring is substituted with an O atom, R 1 and R 2 H and Z are O and R respectively. 3 R is a divalent linear alkylene group containing 2 to 6 carbon atoms, the subscript a is 3, and R 4Each of these is a linear alkyl group containing 1 to 3 carbon atoms.

[0076] In another embodiment of formula (I), X is a heterocyclic group containing two N atoms, and the ring is substituted with an alkyl group containing an O atom in the form of a carbonyl oxygen and one or two carbon atoms, R 1 and R 2 H and Z are O and R respectively. 3 R is a divalent linear alkylene group containing 2 to 6 carbon atoms, the subscript a is 3, and R 4 Each of these is a linear alkyl group containing 1 to 3 carbon atoms.

[0077] In one embodiment, the ureido-functional organosilicon is a ureido-functional silane (i.e., a compound of formula (I) where a' is greater than 0 and b' is 0), and is selected from the following compounds: [ka]

[0078] Some non-restrictive examples of suitable ureidofunctional organosilicon include ureidofunctional silanes represented by the following formula: [ka] [ka] [ka] [ka] [ka] [ka] R in the formula1 and R 2 Each is independently selected from hydrogen and an alkyl group having 1 to 12 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms, and R 3 and R 8 As described above, in embodiments, it is selected from C1-C12 alkylenes, C2-C10 alkylenes, C3-C8 alkylenes, or C4-C6 alkylenes. In embodiments, R 1 and R 2 These are H and R respectively. 3 and R 8 These are each C3 alkylenes.

[0079] In one embodiment, the ureido-functionalized substance is a ureido-functionalized polyorganosiloxane (i.e., a compound of formula (I) where b' is greater than 0 and a' is 0) and has the following formula: M 1 c M 2 d D 1 e D 2 f T 1 g T 2 h Q i During the ceremony: M 1 is (R 16 )(R 17 )(R 18 )SiO 1 / 2 M 2 is (R 19 )(R 20 )(R 21 )SiO 1 / 2 D 1 is (R 22 )(R 23 )SiO 2 / 2 D 2 is (R 24 )(R 25 )SiO 2 / 2 T 1 is (R26 )SiO 3 / 2 T 2 is (R 27 )SiO 3 / 2 Q is SiO 4 / 2 R 16 , R 17 , R 18 , R 22 , R 23 , and R 26 Each is independently R 4 and OR 5 Selected from; R 19 , R 20 , R 21 , R 24 , R 25 , and R 27 Each is independently R 4 , OR 5 and selected from ureido functional groups, provided that R is a condition 19 , R 20 , R 21 , R 24 , R 25 , and R 27 At least one of them is selected from the ureido functional group; Here R 4 The group is independently selected from a monovalent group chosen from a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a cyclic alkyl group having 5 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms; R 5 The group is independently selected from a monovalent group chosen from a linear alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a cyclic alkyl group having 5 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms; d, f, and h are each independently greater than 0; and c, e, g, and i are each independent of each other and are either 0 or greater than 0.

[0080] This composition contains polymer resins. The polymer resins are, but are not limited to, resin polymers such as polyethylene, polypropylene, polyethylene terephthalate, polymethyl methacrylate, aromatic polyamides, chitosan, alginic acid, polyacrylic acid, polyimide, cellulose, and nitrocellulose; rubbery polymers such as SBR (styrene-butadiene rubber), isoprene rubber, butadiene rubber, fluoroelastomers, NBR (acrylonitrile-butadiene rubber), and ethylene propylene rubber; styrene-butadiene styrene block copolymers and their hydrogenation products; thermoplastic elastomer polymers such as EPDM (ethylene The resins include propylene dienthepolymers, styrene ethylene butadiene styrene copolymers, and styrene isoprene styrene block copolymers and their hydrogenation products; flexible resin polymers, such as syndiotactic-1,2-polybutadiene, polyvinyl acetate, ethylene vinyl acetate copolymers, and propylene-α-olefin copolymers; fluoropolymers, such as polyvinylidene fluoride, polytetrafluoroethylene, vinylidene fluoride copolymers, and tetrafluoroethylene-ethylene copolymers; and polymer compositions having ionic conductivity of alkali metal ions (especially lithium ions). The resins may be provided as a single type of resin, or as a mixture of two or more resins when a combination of resins is used, and the resins may be used in any ratio for a particular application.

[0081] This composition optionally contains a binder. Examples of optional binders include, but are not limited to, carboxymethylcellulose, methylcellulose, hydroxymethylcellulose, ethylcellulose, polyvinyl alcohol, oxidized starch, monostarch phosphate, casein, polyvinylpyrrolidone, and salts thereof. The optional binder can be provided as a single material or as a combination of two or more thickeners.

[0082] This composition comprises a polymer resin in an amount of up to about 30% by weight based on the total weight of the electrode composition. In one embodiment, the electrode composition comprises a polymer resin in an amount of up to about 10% by weight based on the total weight of the electrode composition. In one embodiment, the electrode composition comprises a polymer resin in an amount of up to about 4% by weight based on the total weight of the electrode composition.

[0083] In an embodiment, the composition comprises ureido-functional organosilicon in an amount of from about 0.01% by weight to about 90% by weight, from about 0.05% by weight to about 80% by weight, from about 0.1% by weight to about 75% by weight, from about 0.2% by weight to about 60% by weight, from about 0.5% by weight to about 50% by weight, from about 1% by weight to about 25% by weight, or from about 5% by weight to about 10% by weight, based on the total weight of the composition.

[0084] The composition may further comprise an electrode active material, wherein the electrode active material is selected from the group consisting of intercalation agents and conductive agents. The intercalation agent is selected from graphite, lithium nickel manganese cobalt oxide (LiNMC), Si, SiB4, SiB6, Mg2Si, Ni2Si, TiSi2, MoSi2, CoSi2, NiSi2, CaSi2, CrSi2, Cu6Si, FeSi2, MnSi2, NbSi2, TaSi2, VSi2, WSi2, ZnSi2, SiC, Si3N4, Si2N2O, SiO v (0<v≦2), LiSiO, Sn, SnSiO3, LiSnO, and Mg2Sn, SnO wselected from the group consisting of (0<w≦2). In one or more embodiments, the conductive agent is a carbonaceous conductive agent selected from the group consisting of natural graphite, graphite including artificial graphite, acetylene black, ketjen black, channel black, furnace black, lamp black, carbon black including thermal black, amorphous carbon including needle coke, carbon nanotubes, fullerenes, and vapor grown carbon fibers (VGCF). The composition may comprise a single type of conductive agent or two or more conductive agents. The electrode active material is generally used in an amount of about 0.01% by mass or more, about 0.1% by mass or more, about 1% by mass or more, and generally about 50% by mass or less, about 30% by mass or less, more preferably about 15% by mass or less, based on the total mass. An amount of the conductive agent less than the above range may result in insufficient conductivity. In contrast, an amount of the conductive agent exceeding the above range may result in low battery capacity.

[0085] Unexpectedly, it has been found that the ureido-functional organosilicon material provides excellent capacity retention for electrode materials over a large number of charge cycles (i.e., charge / discharge cycles). This was observed both at constant current densities and at variable charge and discharge rates. Materials comprising the ureido-functional organosilicon material also exhibited excellent capacity recovery after reversal of current density. This material also exhibited low impedance over charge and discharge cycles. The ureido-functional organosilicon material also improved the binding properties of the electrode material.

[0086] This composition can be provided as a slurry in combination with a solvent, or as a "dry" solvent-free material. The solvent for forming the slurry may be any solvent capable of dissolving or dispersing the electrode active material, conductive material, and binder, as well as the thickener, if used. The solvent may be either an aqueous solvent or an organic solvent. Examples of aqueous media include water and solvent mixtures of alcohol and water. Examples of suitable organic solvents, but are not limited to, aliphatic hydrocarbons, e.g., hexane; aromatic hydrocarbons, e.g., benzene, toluene, xylene, and methylnaphthalene; heterocyclic compounds, e.g., quinoline and pyridine; ketones, e.g., acetone, methyl ethyl ketone, and cyclohexanone; esters, e.g., methyl acetate and methyl acrylate; amines, e.g., diethylenetriamine and N,N-dimethylaminopropylamine; ethers, e.g., diethyl ether, propylene oxide, and tetrahydrofuran (THF); amides, e.g., N-methylpyrrolidone (NMP), dimethylformamide, and dimethylacetamide; and aprotic polar solvents, e.g., hexamethylphosphoramide and dimethyl sulfoxide.

[0087] This composition is suitable for use in electrochemical devices such as batteries, supercapacitors, fuel cells, and hydrogen storage devices. This electrode composition can be used as part of either a positive or negative electrode material. Electrode materials generally include an electrode active material, such as a positive or negative electrode active material suitable for the desired electrode, a binder composition, and a current collector.

[0088] Compositions containing ureid-functional organosilicon have been found to provide high capacity retention over a relatively large number of electrochemical cycles. In one embodiment, the electrode composition maintains at least 20% of the initial capacity over at least 500 electrochemical cycles in an energy storage device. In one embodiment, the electrode composition maintains at least 40% of the initial capacity over at least 500 electrochemical cycles in an energy storage device. In one embodiment, the binder maintains at least 60% of the initial capacity over at least 500 electrochemical cycles in an energy storage device.

[0089] This composition comprises an electrode active material, where the electrode active material comprises a positive electrode active material and / or a negative electrode active material. The positive electrode active material may be any material capable of electrochemically blocking and releasing lithium ions. Examples of positive electrode active materials include, but are not limited to, lithium-containing transition metal composite oxides, lithium-containing transition metal phosphate compounds, sulfur-based materials, and conductive polymers. Particularly suitable positive electrode active materials are lithium-containing transition metal composite oxides and lithium-containing transition metal phosphate compounds. An exemplary positive electrode active material is a lithium-containing transition metal composite oxide, which generates a high voltage.

[0090] The transition metal in lithium-containing transition metal composite oxides can be selected from V, Ti, Cr, Mn, Fe, Co, Ni, Cu, or others. Specific examples include lithium cobalt composite oxides, e.g., LiCoO2; lithium nickel composite oxides, e.g., LiNiO2; lithium manganese composite oxides, e.g., LiMnO2, LiMn2O4, and Li2MnO4; and those obtained by substituting the transition metal atoms, which are the main components of these lithium transition metal composite oxides, with other elements, e.g., Na, K, B, F, Al, Ti, V, Cr, Mn, Fe, Co, Li, Ni, Cu, Zn, Mg, Ga, Zr, Si, Nb, Mo, Sn, or W. Specific examples of such materials include, but are not limited to, LiNi 0.5 Mn 0.5 O2, LiLiLi 0.85Co 0.10 Al 0.05 O2, LiLiLi 0.5 Co 0.2 Mn 0.3 O2, LiLiLi 0.6 Co 0.2 Mn 0.2 O2, LiLiLi 0.33 Co 0.33 Mn 0.33 O2, LiLiLi 0.8 Co 0.1 Mn 0.1 O2, LiLiLi 0.45 Co 0.10 Al 0.45 O2, LiMn 1.8 Al 0.2 O4 and LiMn 1.5 Ni 0.5 It contains O4.

[0091] LiMn 1.5 Ni 0.5 O4, LiSa 0.5 Co 0.2 Mn 0.3 O2 and LiNi 0.6 Co 0.2 Mn 0.2 O2 is included, and each of these has a high energy density even at high voltages. For voltages of 4.4V or higher, LiMn 1.5 Ni 0.5 O4 is preferred. In order to provide a large-capacity lithium-ion secondary battery, LiNi, a lithium-containing transition metal composite oxide, is preferred. 0.6 Co 0.2 Mn 0.2 O2, LiLiLi 0.8 Co 0.1 Mn 0.1 O2 and LiNi 0.85 Co 0.10 Al 0.05 O2 is particularly suitable.

[0092] The transition metal in lithium-containing transition metal phosphate compounds can be selected from V, Ti, Cr, Mn, Fe, Co, Ni, Cu, or others. Specific examples include iron phosphate, e.g., LiFePO4, Li3Fe2(PO4)3, and LiFeP2O7; cobalt phosphate, e.g., LiCoPO4; and those obtained by substituting some of the transition metal atoms as the main component of these lithium transition metal phosphate compounds with other elements, e.g., Al, Ti, V, Cr, Mn, Fe, Co, Li, Ni, Cu, Zn, Mg, Ga, Zr, Nb, or Si.

[0093] Examples of lithium-containing transition metal composite oxides include those with the formula: Li a Mn 2-b M 1 b Spinel-type lithium manganese composite oxide represented by O4 (where 0.9 ≤ a; 0 ≤ b ≤ 1.5; and M 1 (at least one metal selected from the group consisting of Fe, Co, Ni, Cu, Zn, Al, Sn, Cr, V, Ti, Mg, Ca, Sr, B, Ga, In, Si, and Ge), formula: LiNi 1-c M 2 c Lithium nickel composite oxide represented by O2 (where 0 ≤ c ≤ 0.5; and M 2 (at least one metal selected from the group consisting of Fe, Co, Mn, Cu, Zn, Al, Sn, Cr, V, Ti, Mg, Ca, Sr, B, Ga, In, Si, and Ge), and formula: LiCo 1-d M 3 d Lithium cobalt composite oxide represented by O2 (where 0 ≤ d ≤ 0.5; and M 3 This includes at least one metal selected from the group consisting of Fe, Ni, Mn, Cu, Zn, Al, Sn, Cr, V, Ti, Mg, Ca, Sr, B, Ga, In, Si, and Ge.

[0094] To provide high-power lithium-ion secondary batteries with high energy density, exemplary positive electrode active materials include LiCoO2, LiMnO2, LiNiO2, LiMn2O4, and LiNi0.8 Co 0.15 Al 0.05 O2, or LiNi 1 / 3 Co 1 / 3 Mn 1 / 3 O2.

[0095] Other examples of positive electrode active materials include LiFePO4, LiNi 0.8 Co 0.2 O2, Li 1.2 Fe 0.4 Mn 0.4 O2, LiNi 0.5 Mn 0.5 O2, LiV3O6, and Li2MnO3.

[0096] Examples of sulfur-based materials include materials containing sulfur atoms, such as elemental sulfur, metal sulfides, and organic sulfur compounds. The metal sulfide may be a metal polysulfide. The organic sulfur compound may be an organic polysulfide.

[0097] Examples of metal sulfides include compounds represented by LiS x x (0 < x ≦ 8), compounds represented by Li2S x x (0 < x ≦ 8), compounds having a 2D lamellar structure such as TiS2 and MoS2, and Chevrel compounds having a strong 3D framework structure, for example those represented by the formula: Me x Mo6S8, wherein Me is a transition metal such as Pb, Ag, or Cu.

[0098] Examples of organic sulfur compounds include carbon sulfide compounds.

[0099] Each of the organic sulfur compounds may be supported on a porous substance such as carbon, and thereby used as a carbon composite material. In order to provide better cycle performance and further reduce overvoltage, the amount of sulfur contained in the carbon composite material is 10 to 99% by mass, 20% by mass or more, 30% by mass or more, 40% by mass or more, relative to the mass of the carbon composite material, and in an embodiment, is 85% by mass or less. When the positive electrode active material is elemental sulfur, the amount of sulfur contained in the positive electrode active material is equal to the amount of elemental sulfur contained therein.

[0100] Examples of the conductive polymer include p-type doped conductive polymers and n-type doped conductive polymers. Examples of the conductive polymer include polyacetylene-based polymers, polyphenylene-based polymers, heterocyclic polymers, ionic polymers, ladder polymers, and network polymers.

[0101] In order to improve continuous charging characteristics, the positive electrode active material may contain lithium phosphate. Lithium phosphate may be used in any manner, and can be used as a mixture with the positive electrode active material. The lower limit of the amount of lithium phosphate used is typically 0.1% by mass or more, 0.3% by mass or more, or 0.5% by mass or more, relative to the total amount of the positive electrode active material and lithium phosphate. On the other hand, the upper limit thereof is typically 10% by mass or less, 8% by mass or less, or 5% by mass or less.

[0102] A substance having a different composition from that of the positive electrode active material may be attached to the surface of the positive electrode active material. Examples of the substance attached to the surface include oxides such as aluminum oxide, silicon oxide, titanium oxide, zirconium oxide, magnesium oxide, calcium oxide, boron oxide, antimony oxide, and bismuth oxide; sulfates such as lithium sulfate, sodium sulfate, potassium sulfate, magnesium sulfate, calcium sulfate, and aluminum sulfate; carbonates such as lithium carbonate, calcium carbonate, and magnesium carbonate; and carbon.

[0103] Such substances may be attached to the surface of the positive electrode active material by, for example, dissolving or suspending the substance in a solvent, impregnating the positive electrode active material with this solution or suspension, and drying the impregnated material; dissolving or suspending a precursor of the substance in a solvent, impregnating the positive electrode active material with this solution or suspension, and heating the substance and precursor to induce a reaction between them; or adding the substance to the precursor of the positive electrode active material and sintering these materials simultaneously. For example, when attaching carbon, a carbonaceous material in the form of activated carbon may be mechanically attached to the surface afterward.

[0104] The relative mass of the material adhering to the surface, relative to the amount of positive electrode active material, is typically 0.1 ppm or greater, 1 ppm or greater, or 10 ppm or greater, with upper limits typically less than 20%, less than 10%, or less than 5%. The material adhering to the surface can reduce the oxidation of the electrolyte solution on the surface of the positive electrode active material, thereby improving battery life. If the amount of material is too small, this effect may not be fully provided. If the amount is too large, the movement of lithium ions may be hindered, increasing resistance.

[0105] The particles of the positive electrode active material may have any shape that has been used conventionally, such as bulky, polyhedral, spherical, elliptical, plate-like, needle-like, or columnar. Primary particles may aggregate to form secondary particles.

[0106] The positive electrode active material is typically 1.5 g / cm³. 3 Or higher, 2.0 g / cm³ 3 Or higher, 2.5 g / cm³ 3 or higher, or 3.0 g / cm³ 3Alternatively, it may have a higher tap density. Positive electrode active materials with a tap density below the lower limit may require an increased amount of dispersion medium, and an increased amount of conductive material and binder to form a layer of positive electrode active material, further imposing constraints on the packing density of positive electrode active material in the positive electrode active material layer, and consequently limiting the electrode capacity. Metal composite oxide powders with a high tap density enable the formation of a positive electrode active material layer with high density. Tap density is generally preferred to be as high as possible, and there is no upper limit.

[0107] In this disclosure, tap density refers to the powder packing density (tap density) g / cm³ when 5 to 10 g of positive electrode active material powder is packed into a 10 ml glass graduated cylinder and the graduated cylinder is tapped 200 times with a stroke of approximately 20 mm. 3 It is required as such.

[0108] The positive electrode active material particles may have a median diameter d50 (or secondary particle diameter if primary particles aggregate to form secondary particles) of 0.3 μm or greater, 0.5 μm or greater, 0.8 μm or greater, or 1.0 μm or greater, with upper limits of 30 μm or less, 27 μm or less, 25 μm or less, or 22 μm or less. Particles with a median diameter below this lower limit may not be able to provide a product with high tap density. Particles with a median diameter greater than the upper limit may cause long-term dispersion of lithium within the particles, impairing battery performance and potentially causing streaky defects during positive electrode formation for batteries, for example, when components such as the active material, conductive materials, and additives are formed into a slurry by adding a solvent, and that slurry is applied in the form of a film. Mixing two or more positive electrode active materials with different median diameters d50 can further increase the ease of filling in positive electrode formation.

[0109] In this disclosure, the median diameter d50 is determined using a known laser diffraction / scattering particle size distribution analyzer. When using the LA-920 (Horiba, Ltd.) as the particle size distribution analyzer, the dispersion medium used for measurement is a 0.1 mass% aqueous solution of sodium hexametaphosphate, and the refractive index is set to 1.24 after 5 minutes of ultrasonic dispersion.

[0110] When primary particles aggregate to form secondary particles, the average particle size of the positive electrode active material may be 0.05 μm or larger, 0.1 μm or larger, or 0.2 μm or larger. The upper limit of such aggregates may be 5 μm or less, 4 μm or less, 3 μm or less, or 2 μm or less. Primary particles with an average primary particle size larger than this upper limit have difficulty forming spherical secondary particles and adversely affect powder filling. Furthermore, such primary particles may have a significantly reduced specific surface area, which is likely to impair battery performance, such as output characteristics. In contrast, primary particles with an average primary particle size below the lower limit are usually poorly grown crystals and, for example, have poor charge-discharge reversibility.

[0111] In this disclosure, the primary particle diameter is measured by observation using a scanning electron microscope (SEM). Specifically, the primary particle diameter is determined as follows: First, a photograph is taken at a magnification of 10,000 ×. Fifty primary particles are arbitrarily selected, and the maximum length between the left and right boundary lines of each primary particle is measured along a horizontal line. Next, the average value of these maximum lengths is calculated and defined as the primary particle diameter.

[0112] The positive electrode active material is preferably 0.1 m 2 / g or greater, 0.2m 2 / g or greater, or 0.3m 2 It may have a BET specific surface area of ​​50m / g or greater. 2 / g or less, 40m 2 / g or less, or 30m 2It may be / g or less. Positive electrode active materials with a BET specific surface area smaller than this range can easily impair battery performance. Positive electrode active materials with a BET specific surface area larger than this range will likely not allow for easy increase in tap density and will easily lead to difficulties in applying materials to form the layers of positive electrode active material.

[0113] In this disclosure, the BET specific surface area is defined by a value obtained by the nitrogen adsorption BET single-point method using a gas flow method surface area analyzer (e.g., a fully automated surface area measuring device from Okura Riken Co., Ltd.) with a nitrogen-helium mixed gas whose nitrogen pressure is precisely adjusted to 0.3 relative to atmospheric pressure, and a sample pre-dried in a nitrogen stream at 150°C for 30 minutes.

[0114] The lithium-ion secondary battery of this disclosure is used as a high-capacity lithium-ion secondary battery for hybrid vehicles or distributed power generation and needs to achieve high output. Thus, the particles of the positive electrode active material are preferably composed mainly of secondary particles.

[0115] The positive electrode active material particles have an average secondary particle diameter of 40 μm or less, and may contain 0.5 to 7.0 volume percent of fine particles having an average primary particle diameter of 1 μm or less. The presence of fine particles with an average primary particle diameter of 1 μm or less increases the contact area with the electrolyte solution, allowing for faster diffusion of lithium ions between the electrode and the electrolyte solution, thereby improving the battery's power characteristics.

[0116] The positive electrode active material may be produced by any conventional method for producing inorganic compounds. In particular, spherical or elliptical active materials can be produced by various methods. For example, a transition metal material may be dissolved or pulverized and dispersed in a solvent such as water, and the pH of the solution or dispersion may be adjusted while stirring to form a spherical precursor. This precursor is recovered and dried if necessary. A lithium source, such as LiOH, Li2CO3, or LiNO3, is then added thereto, and the mixture is sintered at a high temperature to provide the active material.

[0117] In the production of a positive electrode, one of the above-mentioned positive electrode active materials may be used alone, or two or more materials having different compositions may be used in any combination and in any ratio. A non-limiting example of a combination is LiCoO₂ and LiMn₂O₄, wherein a part of Mn may be optionally substituted with a different transition metal (for example, LiNi 0.33 Co 0.33 Mn 0.33 O₂), or a combination with LiCoO₂, wherein a part of Co may be optionally substituted with a different transition metal.

[0118] In order to achieve a high battery capacity, the amount of the positive electrode active material is preferably 50 to 99.5% by mass, or 80 to 99% by mass of the positive electrode mixture. The amount of the positive electrode active material in the positive electrode active material layer may be 80% by mass or more, 82% by mass or more, or 84% by mass or more, and the upper limit may be 99% by mass or less, or 98% by mass or less. If the amount of the positive electrode active material in the positive electrode active material layer is too small, the electrical capacity may be insufficient. In contrast, if the amount is too large, the strength of the positive electrode may be insufficient.

[0119] The negative electrode comprises a negative electrode active material layer containing a negative electrode active material and a current collector.

[0120] The negative electrode active material may be any material capable of electrochemically storing and releasing lithium ions. Specific examples thereof include carbon materials, alloy materials, lithium-containing metal composite oxide materials, and conductive polymers. One of these may be used alone, or two or more thereof may be used in any combination.

[0121] Examples of negative electrode active materials include carbonaceous materials capable of blocking and releasing lithium, such as pyrolysis products of organic materials under various thermal decomposition conditions, artificial graphite, and natural graphite; metal oxide materials capable of blocking and releasing lithium, such as tin oxide and silicon oxide; lithium metal; various lithium alloys; and lithium-containing metal composite oxide materials. Two or more of these negative electrode active materials may be used in combination with each other.

[0122] The carbonaceous material capable of blocking and releasing lithium is preferably artificial graphite produced by high-temperature treatment of easily graphitizable pitch from various materials, purified natural graphite, or a material obtained by surface-treating such graphite with pitch or other organic matter and then carbonizing the surface-treated graphite. To achieve a good balance between initial irreversible capacity and rate characteristics at high current densities, the carbonaceous material is more preferably selected from natural graphite, artificial graphite, artificial carbonaceous material, or carbonaceous material obtained by heat-treating artificial graphite material once or more times at 400°C to 3200°C; a carbonaceous material that allows the negative electrode active layer to contain at least two or more carbonaceous materials having different degrees of crystallinity and / or interfaces between carbonaceous materials having different degrees of crystallinity; and a carbonaceous material that allows the negative electrode active layer to have interfaces between at least two or more carbonaceous materials having different orientations. One of these carbonaceous materials may be used alone, or two or more may be used in any combination and any ratio.

[0123] Carbonaceous materials obtained by heat-treating artificial carbonaceous materials or artificial graphite materials once or more at 400°C to 3200°C include coal coke, petroleum coke, coal pitch, petroleum pitch, and products made by oxidizing these pitches; needle coke, pitch coke, and carbon materials made by partially graphitizing these cokes; thermal decomposition products of organic matter such as furnace black, acetylene black, and pitch-based carbon fibers; carbonizable organic matter and its carbides; and solutions prepared by dissolving carbonizable organic matter in low molecular weight organic solvents such as benzene, toluene, xylene, quinoline, or n-hexane, and their carbides.

[0124] The metallic material used as the negative electrode active material (excluding lithium-titanium composite oxide) may be any compound capable of electrochemically blocking and releasing lithium ions, and examples include simple lithium, simple metals and alloys constituting lithium alloys, as well as their oxides, carbides, nitrides, silicides, sulfides, phosphides, etc. The simple metals and alloys constituting lithium alloys are preferably materials containing any metallic and metalloid elements in Groups 13 and 14, more preferably simple metals such as aluminum, silicon, and tin (hereinafter referred to as "specific metallic elements"), and alloys and compounds containing any of these atoms. One of these materials may be used alone, or two or more may be used in any ratio.

[0125] Examples of negative electrode active materials containing at least one atom selected from specific metal elements include simple metals which are any one of the specific metal elements, alloys of two or more specific metal elements, alloys of one or two or more specific metal elements and one or two or more other metal elements, compounds containing one or two or more specific metal elements, and composite compounds such as oxides, carbides, nitrides, silicides, sulfides, and phosphides of these compounds. Such simple metals, alloys, or metallic compounds used as negative electrode active materials can result in high-capacity batteries.

[0126] Further examples include compounds obtained by compositely bonding any of the above composite compounds with several elements, for example, simple metals, alloys, and non-metallic elements. Specifically, for example, in the case of silicon or tin, alloys of such elements with metals that do not function as a negative electrode may be used. For example, in the case of tin, a composite compound comprising a combination of 5 or 6 elements including tin, a metal that functions as a negative electrode (excluding silicon), a metal that does not function as a negative electrode, and a non-metallic element may be used.

[0127] Specific examples of negative electrode active materials include elemental silicon, SiB₄, SiB₆, Mg₂Si, Ni₂Si, TiSi₂, MoSi₂, CoSi₂, NiSi₂, CaSi₂, CrSi₂, Cu₆Si, FeSi₂, MnSi₂, NbSi₂, TaSi₂, VSi₂, WSi₂, ZnSi₂, SiC, Si₃N₄, Si₂N₂O, SiO v (0<v≦2), LiSiO, elemental tin, SnSiO₃, LiSnO, Mg₂Sn, and SnO w (0<w≦2). Examples further include composite materials of Si or Sn used as a first component, and second and third components. The second component is, for example, at least one selected from the group consisting of cobalt, iron, magnesium, titanium, vanadium, chromium, manganese, nickel, copper, zinc, gallium, and zirconium. The third component is, for example, at least one selected from the group consisting of boron, carbon, aluminum, and phosphorus.

[0128] To achieve high battery capacity and excellent battery characteristics, the metal material is preferably elemental silicon or elemental tin (which may contain trace amounts of impurities), SiOv(0<v≦2), SnOw(0≦w≦2), a Si-Co-C composite material, a Si-Ni-C composite material, a Sn-Co-C composite material, or a Sn-Ni-C composite material.

[0129] The lithium-containing metal composite oxide material used as the negative electrode active material may be any material capable of electrochemically blocking and releasing lithium ions. To achieve good rate characteristics at high current densities, materials containing titanium and lithium are preferred, titanium-containing lithium-containing metal composite oxide materials are more preferred, and lithium-titanium composite oxides (hereinafter abbreviated as "lithium-titanium composite oxide") are even more preferred. In other words, the use of a spinel-structured lithium-titanium composite oxide in the negative electrode active material for electrolyte batteries is particularly preferred because it can significantly reduce output resistance.

[0130] Examples of lithium titanium composite oxides include compounds represented by the following formula: Li x Ti y M z O4 Here, M is at least one element selected from the group consisting of Na, K, Co, Al, Fe, Ti, Mg, Cr, Ga, Cu, Zn, and Nb.

[0131] To achieve a good balance of battery performance, the compositions described above are particularly suitable if they satisfy any of the following conditions:

[0132] (i)1.2≦x≦1.4, 1.5≦y≦1.7, z=0

[0133] (ii)0.9≦x≦1.1, 1.9≦y≦2.1, z=0

[0134] (iii)0.7≦x≦0.9, 2.1≦y≦2.3, z=0

[0135] A particularly suitable composition of the compound is Li4 corresponding to composition (i). / 3 Ti 5 / 3 O4, Li1Ti2O4 corresponding to composition (ii), and Li corresponding to composition (iii) 4 / 5 Ti 11 / 5 It is O4. An example of a structure that satisfies Z≠0 is Li 4 / 3 Ti4 / 3 Al 1 / 3 It contains O4.

[0136] The battery may use an electrolyte solution. The electrolyte solution is not particularly limited and can be selected as desired for a specific application or intended use. The electrolyte solution may contain an electrolyte salt and a solvent. For lithium batteries, the electrolyte salt is selected from lithium salts. Examples of lithium salts, but not limited to, are LiPF6, LiBF4, LiClO4, LiAlF4, LiSbF6, LiTaF6, LiWF7, LiAsF6, LiAlCl4, LiI, LiBr, LiCl, and LiB 10 Cl 10Inorganic lithium salts such as Li2SiF6, Li2PFO3, and LiPO2F2; lithium tungstate such as LiWOF5; lithium carboxylates such as HCO2Li, CH3CO2Li, CH2FCO2Li, CHF2CO2Li, CF3CO2Li, CF3CH2CO2Li, CF3CF2CO2Li, CF3CF2CF2CO2Li, and CF3CF2CF2CF2CO2Li; lithium salts containing an S=O group, such as FSO3Li, CH3SO3Li, CH2FSO3Li, CHF2SO3Li, CF3SO3Li, CF3CF2SO3Li, CF3CF2CF2SO3Li, CF3CF2CF2CF2SO3Li, lithium methyl sulfate, lithium ethyl sulfate (C2H5OSO3Li), and lithium ethyl trifluorosulfate (C2H5OSO3Li); lithium imide salts, such as LiN(FCO)2, LiN(FCO)(F SO2), LiN(FSO2)2, LiN(FSO2)(CF3SO2), LiN(CF3SO2)2, LiN(C2F5SO2)2, lithium bis-perfluoroethanesulfonylimide, lithium cyclic 1,2-perfluoroethanedisulfonylimide, lithium cyclic 1,3-perfluoropropanedisulfonylimide, lithium cyclic 1,2-ethanedisulfonylimide, lithium cyclic 1,3-propanedisulfonylimide, lithium cyclic 1,4-perfluorobutanedisulfonylimide, LiN(CF3SO2)(FSO2), LiN(CF3SO2)(C3F7SO2), LiN(CF3SO2)(C4F9SO2), and LiN(POF2)2; lithium methide salts, e.g., LiC(FSO2)3, LiC(CF3SO2)3, and LiC(C2F5SO2)3; and fluorine-containing organolithium salts, e.g., formula: LiPF a (C n F 2n+1 ) 6-aSalts represented by (where a is an integer from 0 to 5; and n is an integer from 1 to 6), such as LiPF3(C2F5)3, LiPF3(CF3)3, LiPF3(iso-C3F7)3, LiPF5(iso-C3F7), LiPF4(CF3)2, and LiPF4(C2F5)2, as well as LiPF4(CF3SO2)2, LiPF4(C2F5SO2)2, LiBF3CF3, LiBF3C2F5, LiBF3C3F7, LiBF2(CF3)2, LiBF2(C2F5)2, LiBF2(CF3SO2)2, and LiBF2(C2F5SO2)2, and LiSCN, LiB(CN)4, LiB(C6H5)4, Li2(C2O4), LiP(C2O4)3, and Li2B 12 F b H 12-b (where b is an integer from 0 to 3)

[0137] The solvent can be any of the following: various non-aqueous compounds, aprotic compounds, and polar organic compounds. Generally, the solvent may be a carbonate, carboxylate, ether, lactone, sulfone, phosphate, nitrile, or ionic liquid. Useful carbonate solvents in this application include, but are not limited to, cyclic carbonates, such as propylene carbonate and butylene carbonate, and linear carbonates, such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, and ethyl propyl carbonate.

[0138] Useful carboxylate solvents include, but are not limited to, methyl formate, ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, and butyl butyrate.

[0139] Useful ethers include, but are not limited to, tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,2-dibutoxyethane, methyl nonafluorobutyl ether, and ethyl nonafluorobutyl ether.

[0140] Useful lactones include, but are not limited to, γ-butyrolactone, 2-methyl-γ-butyrolactone, 3-methyl-γ-butyrolactone, 4-methyl-γ-butyrolactone, β-propiolactone, and δ-valerolactone.

[0141] Useful phosphates include, but are not limited to, trimethyl phosphate, triethyl phosphate, tris(2-chloroethyl) phosphate, tris(2,2,2-trifluoroethyl) phosphate, tripropyl phosphate, triisopropyl phosphate, tributyl phosphate, trihexyl phosphate, triphenyl phosphate, tritlyl phosphate, methyl ethylene phosphate, and ethyl ethylene phosphate.

[0142] Useful sulfones include, but are not limited to, non-fluorinated sulfones, such as dimethyl sulfone and ethyl methyl sulfone; partially fluorinated sulfones, such as methyl trifluoromethyl sulfone, ethyl trifluoromethyl sulfone, methyl pentafluoroethyl sulfone, and ethyl pentafluoroethyl sulfone; and fully fluorinated sulfones, such as di(trifluoromethyl) sulfone, di(pentafluoroethyl) sulfone, trifluoromethyl pentafluoroethyl sulfone, trifluoromethyl nonafluorobutyl sulfone, and pentafluoroethyl nonafluorobutyl sulfone.

[0143] Useful nitriles include, but are not limited to: acetonitrile, propionitrile, butyronitrile, and dinitrile, and CN[CH2] of various alkane chain lengths (n=1~8). n It includes CN.

[0144] Ionic liquids (ILs) are salts in a liquid state. In some contexts, the term is limited to salts whose melting point is below some arbitrary temperature, for example, 100°C (212°F). Ionic liquids are mainly composed of ions and short-lived ion pairs. Common anions in ionic liquids are TFSi, FSi, BOB, and PF. 6-x R x These include BF4 and others, and the cations of the ionic liquids are imidazolium, piperidinium, pyrrolidinium, tetraalkylammonium, morpholinium, and others. Useful ionic liquids include, but are not limited to: bis(oxalate)borate (BOB) anionic liquids, e.g., N-cyanoethyl-N-methylpyrrolidinium BOB, 1-methyl-1-(2-methylsulfoxy)ethyl)pyrrolidinium BOB, and 1-methyl-1-((1,3,2-dioxathiolan-2-oxide-4-yl)methyl)pyrrolidinium BOB; tris(pentafluoroethyl)trifluorophosphate (FAP) anionic liquids, e.g., N-allyl-N-methylpyrrolidinium FAP, N-(oxiran-2-ylmethyl)N-methylpyrrolidinium FAP, and N-(propa-2-yl This includes N-methylpyrrolidinium FAP; bis(trifluoromethanesulfonyl)imide (TFSI) anionic liquids, such as N-propyl-N-methylpyrrolidinium TFSI, 1,2-dimethyl-3-propylimidazolium TFSI, 1-octyl-3-methylimidazolium TFSI, and 1-butylmethylpyrrolidinium TFSI; bis(fluorosulfonyl)imide (FSI) anionic liquids, such as N-butyl-N-methylmorpholinium FSI and N-propyl-N-methylpiperidinium FSI; and other ionic liquids, such as 1-ethyl-3-methylimidazolium tetrafluoroborate.

[0145] Two or more of these solvents may be used in the electrolyte solution. Other solvents may be used as long as they are non-aqueous and aprotic and can dissolve the salt, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, and N,N-dimethyltrifluoroacetamide. Carbonate esters are preferred, most preferably ethylene carbonate (EC), ethylmethyl carbonate (EMC), and mixtures thereof. The amount of solvent is between 70% and 95% of the total electrolyte weight, and more preferably the amount of salt is between 80% and 90% of the total electrolyte weight.

[0146] Examples of electrochemical devices include lithium-ion secondary batteries, lithium-ion capacitors, capacitors such as hybrid capacitors and electric double-layer capacitors, radical batteries, solar cells, especially dye-sensitized solar cells, lithium-ion primary batteries, fuel cells, various electrochemical sensors, electrochromic elements, electrochemical switching elements, aluminum electrolytic capacitors, and tantalum electrolytic capacitors. Lithium-ion secondary batteries, lithium-ion capacitors, and electric double-layer capacitors are preferred. Modules including electrochemical devices are also one aspect of this disclosure.

[0147] The lithium-ion secondary battery may further include a separator. The separator may be formed from any known material and may have any known shape, as long as the resulting separator is stable to the electrolyte solution and has excellent liquid retention properties. The separator is preferably in the form of a porous sheet or nonwoven fabric and is formed from a material that is stable to the electrolyte solution of the Disclosure and has excellent liquid retention properties, such as a resin, glass fiber, or inorganic substance.

[0148] Examples of resin or glass fiber separator materials include polyolefins such as polyethylene and polypropylene, aromatic polyamides, polytetrafluoroethylene, polyethersulfones, and glass filters. One of these materials may be used alone, or two or more may be used in any combination and ratio, for example, in the form of a polypropylene / polyethylene double-layer film or a polypropylene / polyethylene / polypropylene triple-layer film. To achieve good permeability and a good barrier effect for the electrolyte solution, the separator is preferably a porous sheet or nonwoven fabric formed from a polyolefin such as polyethylene or polypropylene.

[0149] The separator may have any thickness, which is typically 1 μm or more, 5 μm or more, or 8 μm or more, and also typically less than 50 μm or less, less than 40 μm or less, or less than 30 μm or less. Separators thinner than these ranges may have insufficient insulation and mechanical strength. Separators thicker than these ranges not only result in unsatisfactory battery performance, such as insufficient rate characteristics, but also reduce the overall energy density of the electrolyte battery.

[0150] Porous separators, such as porous sheets or nonwoven fabrics, may have any porosity. The porosity is typically 20% or greater, preferably 35% or greater, more preferably 45% or greater, while it is typically 90% or less, preferably 85% or less, more preferably 75% or less. Separators with porosity smaller than the above range tend to have high film resistance and insufficient rate characteristics. Separators with porosity larger than the above range tend to have low mechanical strength and insufficient insulation.

[0151] The separator may also have any average pore size. The average pore size is typically 0.5 μm or less, or 0.2 μm or less, while it is typically 0.05 μm or greater. Separators with an average pore size larger than the above range can easily short-circuit. Separators with an average pore size smaller than the above range will have high film resistance and poor rate characteristics.

[0152] Examples of inorganic substances include oxides, such as alumina and silicon dioxide; nitrides, such as alumina nitride and silicon nitride; and sulfides, such as barium sulfate and calcium sulfate, each in the form of particles or fibers.

[0153] The separator is in the form of a thin film, such as a nonwoven fabric, woven fabric, or microporous film. Such thin films preferably have a pore size of 0.01 to 1 μm and a thickness of 5 to 50 μm. Instead of the separate thin film described above, the separator may have a structure in which a composite porous layer containing the inorganic material particles described above is disposed on one or both surfaces of the positive and negative electrodes using a resin binder. For example, alumina particles, 90% of which have a particle size smaller than 1 μm, may be applied to each surface of the positive electrode, and a porous layer may be formed using a fluororesin as a binder.

[0154] <Battery Design>

[0155] The electrode group may be a laminated structure comprising the positive and negative electrode plates described above with the separator in between, or a wound structure comprising the positive and negative electrode plates arranged spirally with the separator in between. The ratio of the volume of the electrode group to the internal volume of the battery (hereinafter referred to as the electrode group ratio) is usually 40% or greater, or 50% or greater, while it is usually 90% or less, or 80% or less.

[0156] In electrode groups having a layered structure, the metal core portions of each electrode layer are preferably bundled together and welded to terminals. When electrodes have a large surface area, the terminal resistance is high. Therefore, it is preferable to arrange multiple terminals within the electrode to reduce this resistance. In electrode groups having a wound structure, multiple lead structures may be arranged on both the positive and negative electrodes and bundled together to terminals. This can reduce internal resistance.

[0157] The outer case may be made from any material that is stable to the electrolyte solution used. Specific examples include nickel-plated steel plates, stainless steel, aluminum and aluminum alloys, magnesium alloys, and laminated films of resin and aluminum foil. To reduce weight, metals such as aluminum or aluminum alloys, or laminated films, are preferably used.

[0158] An outer case made of metal may have a sealed structure formed by welding metal by laser welding, resistance welding, or ultrasonic welding, or a crimped structure using metal with a resin gasket in between. An outer case made of laminate film may have a sealed structure formed by thermally melting a resin layer. To improve the sealing performance, a resin different from the resin of the laminate film may be placed between the resin layers. In particular, when a sealed structure is formed by thermally melting a resin layer with a current collector terminal in between, the metal and resin will be bonded together. Thus, the resin placed between the resin layers is preferably a resin having polar groups, or a modified resin having introduced polar groups.

[0159] The lithium-ion secondary battery of this disclosure may have any shape, for example, cylindrical, square, stacked, coin (button) shaped, or large diameter. The shape and structure of the positive electrode, negative electrode, and separator may be modified according to the shape of the battery.

[0160]

[0161] Examples

[0162] The manufacture of electrodes for lithium-ion coin batteries involves a negative electrode active material and the composition of the present invention. As a comparative electrode composition, the composition contains styrene-butadiene rubber (SBR) and carboxymethylcellulose (CMC). For the test formulation, a ureid-functional organosilicon material (also known as UPY in the examples of this application) was added to the SBR / CMC mixture. In all cases, a slurry was prepared by adding the required amount of water. The active material for the slurry contained graphite, silicon monoxide, and carbon black in a ratio of 80:14:1. The remaining 5% by weight of this composite contained the composition of the present invention, which included a polymer, a ureid-functional organosilicon material, and an electrode active material. A comparative electrode composition containing SBR and CMC in a ratio of 3:2 was deemed to have an appropriate ratio, resulting in a coating that was well integrated onto the current collector surface. In the tested samples, ureid-functional organosilicon material was used together with SBR and CMC in a ratio of SBR / CMC / ureid-functional material = 2:1:1 to obtain a coating on the current collector. In a 100-gram test sample, 1 gram of UPY (1 wt%) was used per total weight of the electrode composition, along with 2 grams of SBR (2 wt%) and 1 gram of CMC (1 wt%).

[0163] The electrode slurry was prepared in a speed mixer, where, in the first step, the respective amounts of electrode active material, graphite, and carbon black were mixed with silicon monoxide for one minute at 2000 rpm. This mixing was repeated three times to achieve a homogeneous mixture. Next, a calculated amount of SBR was added and mixed again three times at 2000 rpm, and the development of viscosity in the complex was observed. Subsequently, CMC and a calculated amount of additives were added and mixed three times at 2000 rpm in the speed mixer. Finally, the required amount of water was added to obtain a viscous slurry that could be coated onto the electrode. Homogeneous mixing of the water was also ensured by mixing three times at 2000 rpm in the speed mixer.

[0164] The slurry was then coated onto the surface of the current collector, which was 50 μm thick, using a wire coater. This coated foil was then dried in a vacuum oven at 110°C for 6 hours, and coins were then cut from this foil for assembling 2032 coin batteries.

[0165] In the case of dry coating technology, the required amount of negative electrode active material, including graphite, silicon monoxide, and carbon black, was first mixed with a binder containing a nitrogen-containing silane additive. This composition was mixed at 120°C for 4 hours. The mixture was then passed over the metal foil of the current collector through twin-axis rollers at high temperature, resulting in the formation of a coating on the current collector. Following the formation of this coating, coins were cut from the foil and assembled into coin cells as described below.

[0166] The lithium-ion battery was manufactured inside an argon-filled glove box, using lithium as the counter electrode, LiPF6(1M) / EC / EMC as the electrolyte, and a Celgard separator. The battery was analyzed using Biologic's BCS805 to determine its electrochemical properties.

[0167] Electrochemical analysis of ureid-functional organosilicon materials (UPY) to SBR / CMC formulations was performed in 2032 lithium-ion coin cells. The working electrode contained graphite / SiO / CB, where carbon black (CB) was added as a conductivity-enhancing component. As previously described, the coin cell was assembled inside an argon-filled glove box, and a solvent-free lithium coin was used as the counter electrode. Initially, a cyclic voltammogram (CV) was recorded between 3.0 and 0.1 V, and 10 charge / discharge cycles were recorded. The initial discharge curve showed the presence of a trough between 1.4 and 1.1 V, suggesting the formation of an SEI layer. A large drop was also recorded below 0.6 V, which is attributed to the intercalation of lithium ions along the interstitial positions and edges of the graphite. Figure 1 shows the ureid-functional organosilicon material (UPY) with the following equation: [ka] This shows a cyclic voltammogram of a graphite / SiO / CB electrode equipped with [the specified feature].

[0168] The corresponding charge cycle shows a bump around ~0.5V, which is attributed to the elimination of lithium ions from the graphite / SiO matrix. Subsequent charge / discharge cycles show high reproducibility, indicating the high stability of this electrode and representing its mechanical integrity. The high stability of an electrode with a highly expandable material can be attributed to an efficient binder formulation that helps maintain the mechanical integrity of the electrode. No troughs were present between the second and subsequent discharge cycles, suggesting that SEI formation was limited to the first discharge cycle.

[0169] Furthermore, a CV (Cyclical Voltage Computation) was performed on a reference battery, and the following points were noted: While the peak fingerprint region appeared in a similar voltage range, indicating similar electrochemical activity, the CV curve of the reference binder recorded a lower current density. In addition, instability during the charging cycle was recorded, indicating inferior performance of the reference binder. The effect of the additive is related to the long-term cycle stability and capacity retention of the electrodes. Figure 2 shows the cyclic voltammogram of a battery containing graphite / SiO / CB electrodes using an SBR / CMC binder without additives.

[0170] Cycle stability was tested over 500 cycles at a current rate of 50 mA / g, and the calculated specific capacitance is shown in Table 2. [Table 1] The capacities at different cycle counts were calculated and shown in Table 1. It is noteworthy that at the end of 500 cycles, the capacity of the electrode composition of the present invention (2nd column) maintained 77% of its initial capacity (3rd column, 6th row). In contrast, the reference composition (4th column in Table 1) was only able to retain 10% of its initial capacity after 500 cycles. Figure 3 shows the charge / discharge curves for various cycle counts.

[0171] The above description includes examples provided herein. Of course, for the purposes of this specification, it is impossible to describe all recognizable combinations of components or methodologies, but those skilled in the art will recognize that many further combinations and substitutions of this specification are possible. Thus, this specification is intended to encompass all such changes, modifications and variations that are included within the idea and scope of the appended claims. Furthermore, wherever the term “encompasses” is used in the detailed description or claims, such term is intended to be as comprehensive as “includes,” as is the case when “includes” is used as a substitute in the claims.

[0172] The above description illustrates various non-limiting embodiments of binder materials for use in electrochemical apparatus and examples of their applications. Modifications may be conceived by those skilled in the art and those who create and use the present invention. The disclosed embodiments are for illustrative purposes only and are not intended to limit the scope of the invention or subject matter described in the claims.

Claims

1. A composition: (a) Polymer resins; (b) Compounds represented by formula (I): 【Chemistry 26】 wherein R １ ', R ２ ', R ３ ', R ４ ', R ５ ', and R ６ ' are each independently selected from the group consisting of R ４ , OR ５ , and a ureido functional group, wherein R ４ is each independently selected from monovalent groups selected from the group consisting of linear alkyl having 1 to 12 carbon atoms, branched alkyl having 3 to 12 carbon atoms, cyclic alkyl having 5 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, aryl groups having 6 to 20 carbon atoms, and aralkyl having 7 to 20 carbon atoms; R ５ is each independently selected from monovalent groups selected from the group consisting of linear alkyl having 1 to 12 carbon atoms, branched alkyl having 3 to 12 carbon atoms, cyclic alkyl having 5 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, aryl groups having 6 to 20 carbon atoms, and aralkyl having 7 to 20 carbon atoms; a' or b' is between 0 and 500, provided that at least one of these a' or b' is > 0; and R １ ', R ２ ', R ３ ', R ４ ', R ５ ', and / or R ６ At least one of them is a ureid functional group; Here, the ureido functional group is represented by the following equation: 【Chemistry 27】 In the formula R １ and R ２ Each is independently selected from the group consisting of a monovalent organic group having hydrogen and 1 to 20 carbon atoms; R ３ is a divalent linear alkylene group having 1 to 20 carbon atoms, or a divalent branched alkylene group having 3 to 20 carbon atoms, each optionally containing one or more heteroatoms in the chain; X is selected from the group consisting of substituted or unsubstituted aromatic groups having 6 to 20 carbon atoms and heterocyclic groups containing 1 to 20 heteroatoms, where the aromatic group and / or heterocyclic group is optionally substituted with an alkyl group having 1 to 12 carbon atoms and optionally containing heteroatoms and ureid functional groups optionally selected from the group consisting of O, N, and / or S; and Z is oxygen; (c) Electrode active material; and (d) A binder of any choice A composition containing the following:

2. The composition of claim 1, wherein the polymer resin is selected from one or more of the group consisting of polyethylene, polypropylene, polyethylene terephthalate, polymethyl methacrylate, aromatic polyamide, chitosan, alginic acid, polyacrylic acid, polyimide, cellulose, carboxymethylcellulose, nitrocellulose; styrene-butadiene rubber (SBR), isoprene rubber, butadiene rubber, fluoroelastomer, acrylonitrile butadiene rubber (NBR), ethylene propylene rubber; styrene-butadiene styrene block copolymer and its hydrogenation products; EPDM (ethylene propylene dienterpolymer), styrene-ethylene butadiene styrene copolymer, styrene-isoprene styrene block copolymer and its hydrogenation products; syndiotactic-1,2-polybutadiene, polyvinyl acetate, ethylene vinyl acetate copolymer, and propylene-α-olefin copolymer; polyvinylidene fluoride, polytetrafluoroethylene, vinylidene fluoride copolymer, and tetrafluoroethylene-ethylene copolymer; and polymers containing alkali metal ions.

3. The composition of claim 1 or 2, wherein the optionally selected binder is one or more selected from the group consisting of carboxymethylcellulose, methylcellulose, hydroxymethylcellulose, ethylcellulose, polyvinyl alcohol, oxidized starch, monostarch phosphate, casein, polyvinylpyrrolidone, and salts thereof.

4. The electrode active material is selected from the group consisting of one or more inserts and conductive agents, according to any one of claims 1 to 3.

5. The inserts are graphite, lithium nickel manganese cobalt oxide (LiNMC), Si, SiB ４ SiB ６ Mg ２ Si, Ni ２ Si, TiSi ２ MoSi ２ CoSi ２ NiSi ２ CaSi ２ , CrSi ２ ,Cd ６ Si, FeSi ２ , MnSi ２ NbSi ２ , TaSi ２ , VSi ２ , WSi ２ ZnSi ２ SiC, Si ３ N ４ Si ２ N ２ O, SiO ｖ (0<v≦2), LiSiO, Sn, SnSiO ３ , LiSnO, and Mg ２ Sn, SnO ｗ The composition of claim 4, selected from the group consisting of (0 < w ≤ 2).

6. The composition of claim 4 or 5, wherein the conductive agent is a carbonaceous conductive agent selected from the group consisting of natural graphite, graphite including artificial graphite, carbon black including acetylene black, Ketjen black, channel black, furnace black, lamp black, and thermal black, amorphous carbon including needle coke, carbon nanotubes, fullerene, and vapor-grown carbon fiber (VGCF).

7. The composition according to any one of claims 1 to 6, wherein the condition is a' > 0, b' = 0, and the compound represented by formula (I) is a polysilane.

8. The compound of formula (I) has the formula: 【Chemistry 28】 It has R in the formula １’ , R ３’ , R ５’ , and R ６’ Each is independently R ４ , OR ５ Selected from , and ureido functional groups, where R ４ The group is independently selected from monovalent groups selected from linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, cyclic alkyl groups having 5 to 12 carbon atoms, alkenyl groups having 2 to 12 carbon atoms, aryl groups having 6 to 20 carbon atoms, and aralkyl groups having 7 to 20 carbon atoms; R ５ The group is independently selected from monovalent groups selected from linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, cyclic alkyl groups having 5 to 12 carbon atoms, alkenyl groups having 2 to 12 carbon atoms, aryl groups having 6 to 20 carbon atoms, and aralkyl groups having 7 to 20 carbon atoms; a' is 1 to 500; and R １’ , R ３’ , R ５’ , and R ６’ The composition of claim 7, wherein at least one of is selected from ureid functional groups.

9. The composition according to any one of claims 1 to 6, wherein the condition is b' > 0, provided a' = 0, and the compound represented by formula (I) is a polysiloxane.

10. The composition according to any one of claims 1 to 9, wherein the compound represented by formula (I) is a ureido-functional organosilicon.

11. The formula for ureido-functional organosilicon is: 【Chemistry 29】 It is a compound of the formula, and in the formula R １ and R ２ Each is a monovalent organic group having either hydrogen or 1 to 20 carbon atoms independently; R ３ These are divalent linear alkylene groups having 1 to 20 carbon atoms, or divalent branched alkylene groups having 3 to 20 carbon atoms, each optionally containing one or more heteroatoms in the chain; R ４ This is independently a monovalent group selected from the group consisting of linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, cyclic alkyl groups having 5 to 12 carbon atoms, alkenyl groups having 2 to 12 carbon atoms, aryl groups having 6 to 20 carbon atoms, and aralkyl groups having 7 to 20 carbon atoms; R ５ These are independently selected from the group consisting of linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, cyclic alkyl groups having 5 to 12 carbon atoms, alkenyl groups having 2 to 12 carbon atoms, aryl groups having 6 to 20 carbon atoms, and aralkyl groups having 7 to 20 carbon atoms; X is an aromatic group having 6 to 20 carbon atoms or a heterocyclic group containing up to 20 heteroatoms, where the aromatic group or heterocyclic group is optionally substituted with an alkyl group having 1 to 12 carbon atoms, optionally containing a heteroatom selected from the group consisting of O, N, and / or S, and a ureid functional group: Z is oxygen; and A composition according to any one of claims 1 to 10, wherein a is an integer having a value of 1, 2, or 3.

12. The compound of formula (I) is a polysiloxane represented by the following formula: M １ ａ M ２ ｂ D １ ｃ D ２ ｄ T １ ｅ T ２ ｆ Q ｇ During the ceremony: M １ is (R １６ ) (Caution １７ ) (Caution １８ ) SiO １／２ M ２ is (R １９ ) (Caution ２０ ) (Caution ２１ ) SiO １／２ D １ is (R ２２ ) (Caution ２３ ) SiO ２／２ D ２ is (R ２４ ) (R ２５ )SiO ２／２ T １ is (R ２６ ) SiO ３／２ T ２ is (R ２７ )SiO ３／２ Q is SiO ４／２ R １６ , R １７ , R １８ , R ２２ , R ２３ , and R ２６ R is independent ４ and OR ５ Selected from the group consisting of; R １９ , R ２０ , R ２１ , R ２４ , R ２５ , and R ２７ R is independent ４ , OR ５ Selected from the group consisting of and ureido functional groups, provided that R is a condition １９ , R ２０ , R ２１ , R ２４ , R ２５ , and R ２７ At least one of them is a ureid functional group; Here R ４ The group is independently selected from the group consisting of monovalent groups selected from linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, cyclic alkyl groups having 5 to 12 carbon atoms, alkenyl groups having 2 to 12 carbon atoms, aryl groups having 6 to 20 carbon atoms, and aralkyl groups having 7 to 20 carbon atoms; R ５ These are independently selected from the group consisting of linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, cyclic alkyl groups having 5 to 12 carbon atoms, alkenyl groups having 2 to 12 carbon atoms, aryl groups having 6 to 20 carbon atoms, and aralkyl groups having 7 to 20 carbon atoms; b, d, and f are independent integers greater than 0; and The composition according to any one of claims 1 to 6 or 9, wherein a, c, e, and g are each independently integers greater than 0.

13. A composition according to any one of claims 1 to 12, wherein X is a six-membered ring containing up to five nitrogen atoms.

14. A composition according to any one of claims 1 to 12, wherein X is a six-membered ring containing one or two nitrogen atoms.

15. X is: 【Transformation 30】 Selected from, here R １１ A composition according to any one of claims 1 to 12, wherein is selected from the group consisting of hydrogen and a monovalent organic group having 1 to 12 carbon atoms.

16. X is: 【Chemistry 31】 And here J １ J ２ , and J ３ Each of these is independently a substituted or unsubstituted C atom or N atom, and J １ J ２ , and J ３ The dashed line between them is J １ and J ２ or J ２ and J ３ This shows an optional double bond between them. A composition according to any one of claims 1 to 12.

17. The substituents in X are represented by the following equation: 【Chemistry 32】 In the formula R ６ and R ７ Each is a monovalent organic group having either hydrogen or 1 to 20 carbon atoms independently; R ８ This is a divalent linear alkylene group having 1 to 20 carbon atoms, or a divalent branched alkylene group having 3 to 20 carbon atoms, each of which can optionally contain one or more heteroatoms in the chain; R ９ Each is independently selected from the group consisting of monovalent groups selected from linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, cyclic alkyl groups having 5 to 12 carbon atoms, alkenyl groups having 2 to 12 carbon atoms, aryl groups having 6 to 20 carbon atoms, and aralkyl groups having 7 to 20 carbon atoms; R １０ is independently selected from monovalent groups selected from linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, cyclic alkyl groups having 5 to 12 carbon atoms, alkenyl groups having 2 to 12 carbon atoms, aryl groups having 6 to 20 carbon atoms, and aralkyl groups having 7 to 20 carbon atoms; and here The composition according to any one of claims 1 to 12, wherein b is an integer having a value of 1, 2, or 3.

18. The composition of claim 17, wherein the ureido-functional organosilicon is represented by the following formula. 【Transformation 33】

19. The composition according to any one of claims 1 to 18, wherein the compound represented by formula (I) is present in an amount of about 0.1 to 10% by weight based on the total weight of the composition.

20. The composition according to any one of claims 1 to 18, wherein the compound of formula (I) is present in an amount of about 0.01% to about 90% by weight, about 0.05% to about 80% by weight, about 0.1% to about 75% by weight, about 0.2% to about 60% by weight, about 0.5% to about 50% by weight, about 1% to about 25% by weight, or about 5% to about 10% by weight, based on the total weight of the composition; preferably, it is present in an amount of 1 to 10% by weight, 10 to 50% by weight, or 50 to 90% by weight, based on the total weight of the composition.

21. A composition which is a solvent-free composition, any one of claims 1 to 19.

22. An energy storage device: (a) at least one electrode; and (b) An energy storage device comprising an electrolyte, wherein at least one electrode comprises a composition of any of claims 1 to 21.

23. The energy storage device according to claim 22, wherein the specific capacity determined by a cycle stability test after at least 500 electrochemical cycles is at least 20% of the specific capacity after the first cycle.

24. The energy storage device according to claim 22 or 23, wherein the specific capacity determined by a cycle stability test after at least 500 electrochemical cycles is at least 40% of the specific capacity after the first cycle.

25. An energy storage device according to any one of claims 22 to 24, wherein the specific capacity determined by a cycle stability test after at least 500 electrochemical cycles is at least 60% of the specific capacity after the first cycle.

26. An energy storage device according to any one of claims 22 to 25, wherein the device is a secondary battery.

27. The energy storage device according to claim 26, wherein the secondary battery is a lithium-ion battery.

28. An energy storage device comprising: at least one electrode and an electrolyte, wherein the at least one electrode comprises: (a) a polymer resin; (b) a capacity retainer; (c) an electrode active material; and (d) optionally a binder, wherein the capacity retainer maintains the specific capacity of the electrode in the range of at least 20 to 80% of the specific capacity after the first cycle after 500 electrochemical cycles.

29. The volume-retaining agent has the following formula: 【Transformation 34】 It is expressed by, where R １ ', R ２ ', R ３ ', R ４ ', R ５ ', and R ６ Each of them is R ４ , OR ５ , or a ureido functional group, where R ４ These are independently linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, cyclic alkyl groups having 5 to 12 carbon atoms, alkenyl groups having 2 to 12 carbon atoms, and aryl groups having 6 to 20 carbon atoms, or aralkyl groups having 7 to 20 carbon atoms; R ５ These are independently linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, cyclic alkyl groups having 5 to 12 carbon atoms, alkenyl groups having 2 to 12 carbon atoms, aryl groups having 6 to 20 carbon atoms, or aralkyl groups having 7 to 20 carbon atoms; a' or b' are integers whose values ​​are between 0 and 500, provided that at least one of a' or b' is > 0; and R １ ', R ２ ', R ３ ', R ４ ', R ５ ', and / or R ６ The energy storage device of claim 28, wherein at least one of the ' is a ureid functional group.

30. The ureido functional group has the formula: 【Chemistry 35】 It is expressed by, where R １ and R ２ Each is independently selected from the group consisting of a monovalent organic group having hydrogen and 1 to 20 carbon atoms; R ３ These are divalent linear alkylene groups having 1 to 20 carbon atoms, or divalent branched alkylene groups having 3 to 20 carbon atoms, each optionally containing one or more heteroatoms in the chain; X is selected from the group consisting of substituted or unsubstituted aromatic groups having 6 to 20 carbon atoms and heterocyclic groups containing 1 to 20 heteroatoms, where the aromatic group and / or heterocyclic group is optionally substituted with an alkyl group having 1 to 12 carbon atoms and optionally containing a heteroatom and a ureid functional group, which are optionally selected from the group consisting of O, N, and / or S: and The energy storage device according to claim 29, wherein Z is oxygen.

31. An electrode comprising any one composition of claim 1 to 21.

32. An electrochemical battery comprising a negative electrode and a positive electrode, wherein the negative electrode, the positive electrode, or both the negative electrode and the positive electrode comprises the composition of claims 1 to 21.

33. Furthermore, the electrochemical battery according to claim 32, including a separator.

34. The electrochemical battery according to claim 32 or 33, wherein the electrochemical battery is a lithium-ion battery.

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