Composition for electrode

Abstract

Compositions suitable for use in electrochemical devices are shown and described herein. The compositions include an organic functional material having a nitrogen functionality. In aspects, the nitrogen functionality is a urea-based functionality. The compositions can be used in electrode materials employed in electrochemical cells, such as, for example, lithium batteries.

Description

Technical Field

[0001] This invention relates to compositions for use as electrodes. Specifically, this invention relates to compositions comprising urea-functionalized compounds as additives and compositions suitable for forming electrodes. Background Technology

[0002] As the use of batteries increases in various applications (such as electric vehicles and consumer electronics), the demand for the development and improvement of energy generation and storage devices continues to grow. Manufacturers want to provide improved characteristics for battery packs, such as high capacity, fast charging, long range, and long storage life. These characteristics are directly affected by the electrochemical reactions that occur inside the battery cell.

[0003] Graphite is a common material used in anode materials. Graphite has an irreversible capacity of 372 mAh g⁻¹. This limited capacity hinders its application in next-generation high-capacity battery packs that can operate for extended periods on a single charge.

[0004] Lithium-ion battery packs have garnered significant attention and use in industry. One way to increase the capacity of lithium-ion battery packs is through the use of high-capacity materials and graphite doping or the development of composites. Potential anode 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 demonstrate capacities up to 3700 mAh g⁻¹. Silicon monoxide can provide capacities of approximately 1850 mAh g⁻¹.

[0005] However, silicon exhibits high expansion during lithiation. The volume of silicon can expand by up to 400% compared to its initial size. This can lead to electrode cracking and capacity reduction. Silicon also undergoes significant pulverization during the reaction with lithium, resulting in substantial irreversible capacity loss. This also leads to capacity reduction (or decay) with charge cycles in the battery pack. Summary of the Invention

[0006] The following is an overview of this disclosure to provide a basic understanding of some aspects. This overview is not intended to identify key or essential elements, nor does it limit the implementation or any aspects of the claims. Furthermore, this overview provides a brief overview of some aspects that can be described in more detail in other parts of this disclosure.

[0007] The provided material is a composition suitable for electrodes. The composition comprises a nitrogen-containing organosilicon material as an additive. In this embodiment, the nitrogen-containing organosilicon material is a urea-functionalized organosilicon material. Urea-functionalized organosilicon materials have been found to provide excellent capacity retention for electrode materials over a large number of charge cycles (i.e., charge / discharge cycles). This is observed at both constant current densities and different rate operations. Materials containing urea-functionalized organosilicon materials also exhibit excellent capacity recovery after reversing the current density. These materials also exhibit low impedance during cycling.

[0008] In one aspect, a composition is provided comprising:

[0009] (a) Polymer resin,

[0010] (b) Compounds represented by formula (I)

[0011] (I)

[0012] Where R 1' R 2' R 3' R 4' R 5' and R 6' Independently selected from R 4 OR 5 and urea functional groups, wherein R 4 Independently selected from monovalent groups, said monovalent group being selected from straight-chain alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, cycloalkyl 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, which are selected from straight-chain alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, cycloalkyl 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.

[0013] a' or b' is 0-500, provided that at least one of these a' or b' is greater than 0; and at least one R 1' R 2' R 3' R 4' R 5' and / or R 6' It has a urea functional group;

[0014] The urea functional group therein is represented by the following formula:

[0015]

[0016] Where R 1 and R 2 Each is independently selected from hydrogen and monovalent organic groups having 1 to 20 carbon atoms;

[0017] R 3 It is a divalent straight-chain alkylene group having 1 to 20 carbon atoms, or a divalent branched alkylene group having 3 to 20 carbon atoms, each of which optionally contains one or more heteroatoms within the chain; X is selected from substituted or unsubstituted aromatic groups having 6 to 20 carbon atoms and heterocyclic groups containing 1 to 20 heteroatoms, wherein the aromatic groups and / or the heterocyclic groups are optionally substituted with alkyl groups having 1 to 12 carbon atoms, and optionally contain heteroatoms selected from O, N and / or S, and a ureidofunctional group; and wherein Z is oxygen;

[0018] (c) Electrode activators; and

[0019] (d) Optional adhesive.

[0020] In one embodiment, the polymer resin is selected from one or more of the following: polyethylene, polypropylene, polyethylene terephthalate, polymethyl methacrylate, aromatic polyamide, chitosan, alginate, polyacrylic acid, polyimide, cellulose, carboxymethyl cellulose, nitrocellulose; styrene-butadiene rubber (SBR), isoprene rubber, butadiene rubber, fluorinated elastomers, acrylonitrile-butadiene rubber (NBR), ethylene-propylene rubber; styrene-butadiene-styrene block copolymers and their hydrogenated products; EPDM (ethylene-propylene-diene terpolymer), styrene-ethylene-butadiene-styrene copolymer, styrene-isoprene-styrene block copolymers and their hydrogenated products; syndiotactic 1,2-polybutadiene, polyvinyl acetate, ethylene-vinyl acetate copolymers and propylene-α-olefin copolymers; polyvinylidene fluoride, polytetrafluoroethylene, vinylidene fluoride copolymers and tetrafluoroethylene-ethylene copolymers; and polymers containing alkali metal ions.

[0021] In any of the foregoing embodiments, the optional binder is selected from one or more of the following: carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, oxidized starch, monostarch phosphate, casein, polyvinylpyrrolidone, and their salts.

[0022] In any of the foregoing embodiments, the electrode activator is selected from one or more of an intercalating agent and a conductive agent. In one embodiment, the intercalating 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, and SiO. v (0 < v≦ 2), LiSiO, Sn, SnSiO3, LiSnO and Mg2Sn, SnO w (0 < w ≦ 2).

[0023] In one embodiment, the conductive agent is a carbonaceous conductive agent selected from graphite, including natural graphite and artificial graphite; carbon black, including acetylene black, Ketjen black, channel black, furnace black, lamp black, and thermal cracking black; amorphous carbon, including needle coke; carbon nanotubes; fullerenes; and vapor-grown carbon fibers (VGCF).

[0024] In any of the foregoing embodiments, a'>0, provided that b'=0, and the compound represented by Formula 1 is a polysilane.

[0025] In any of the foregoing embodiments, the compound of formula (I) has the following formula:

[0026]

[0027] Where R 1' R 3' R 5' and R 6' Each independently selected from R 4 OR 5 and urea functional groups, wherein R 4 The group is independently selected from monovalent groups, which are selected from straight-chain alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, cycloalkyl 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.

[0028] R 5The group is independently selected from monovalent groups, which are selected from straight-chain alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, cycloalkyl 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.

[0029] a' is 1-500; and

[0030] R 1' R 3' R 5' and R 6' At least one of them is selected from the urea functional group.

[0031] In any of the foregoing embodiments, b'>0, provided that a'=0, and the compound represented by Formula 1 is a polysiloxane.

[0032] In any of the foregoing embodiments, the compound represented by Formula 1 is a urea-functionalized organosilicon.

[0033] In any of the foregoing embodiments, the urea-functionalized organosilicon is a compound of the following formula:

[0034]

[0035] in,

[0036] R 1 and R 2 Each is independently hydrogen or a monovalent organic group having 1 to 20 carbon atoms;

[0037] R 3 It is a divalent straight-chain alkylene having 1 to 20 carbon atoms, or a divalent branched alkylene having 3 to 20 carbon atoms, each of which optionally contains one or more heteroatoms within the chain;

[0038] R 4 Independently, it is a monovalent group selected from the following: straight-chain alkyl having 1 to 12 carbon atoms, branched alkyl having 3 to 12 carbon atoms, cycloalkyl having 5 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, aryl having 6 to 20 carbon atoms, and aralkyl having 7 to 20 carbon atoms;

[0039] R 5 It is independently selected from straight-chain alkyl having 1 to 12 carbon atoms, branched alkyl having 3 to 12 carbon atoms, cycloalkyl having 5 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, aryl having 6 to 20 carbon atoms, and aralkyl having 7 to 20 carbon atoms;

[0040] X is an aromatic group having 6 to 20 carbon atoms or a heterocyclic group containing up to 20 heteroatoms, wherein the aromatic group or heterocyclic group is optionally substituted with an alkyl group having 1 to 12 carbon atoms, and optionally contains a heteroatom selected from O, N and / or S, and a urea functional group:

[0041] Z is oxygen; and

[0042] a is an integer with the value 1, 2, or 3.

[0043] In any of the foregoing embodiments, the compound of formula (I) is a polysiloxane represented by the following formula:

[0044] M 1 a M 2 b D 1 c D 2 d T 1 e T 2 f Q g

[0045] in:

[0046] M 1 For (R) 16 (R) 17 (R) 18 SiO 1 / 2

[0047] M 2 For (R) 19 (R) 20 (R) 21 SiO 1 / 2

[0048] D 1 For (R) 22 (R) 23 SiO 2 / 2

[0049] D 2 For (R) 24 (R) 25 SiO 2 / 2

[0050] T 1 For (R) 26 SiO 3 / 2

[0051] T 2 For (R) 27 SiO3 / 2

[0052] Q is SiO 4 / 2

[0053] R 16 R 17 R 18 R 22 R 23 and R 26 Independently selected from R 4 and OR 5 ;

[0054] R 19 R 20 R 21 R 24 R 25 and R 27 Independently selected from R 4 OR 5 and urea functional group, condition is R 19 R 20 R 21 R 24 R 25 and R 27 At least one of them is a urea functional group;

[0055] Where R 4 The group is independently selected from monovalent groups, which are selected from straight-chain alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, cycloalkyl 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.

[0056] R 5 It is independently selected from straight-chain alkyl having 1 to 12 carbon atoms, branched alkyl having 3 to 12 carbon atoms, cycloalkyl having 5 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, aryl having 6 to 20 carbon atoms, and aralkyl having 7 to 20 carbon atoms;

[0057] b, d, and f are independent integers greater than 0; and

[0058] a, c, e, and g are each an independent integer greater than 0.

[0059] In any of the foregoing embodiments, X is a six-membered ring containing up to five nitrogen atoms.

[0060] In any of the foregoing embodiments, X is a six-membered ring containing one or two nitrogen atoms.

[0061] In any of the foregoing embodiments, X is selected from...

[0062] ; ; ;and

[0063] Where R 11 Selected from hydrogen and monovalent organic groups having 1 to 12 carbon atoms.

[0064] In any of the foregoing embodiments, X is...

[0065]

[0066] J1, J2, and J3 are each independently a substituted or unsubstituted C or N atom, and the dashed line between J1, J2, and J3 represents an optional double bond between J1 and J2 or between J2 and J3.

[0067] In any of the foregoing embodiments, the substituent in X is represented by the following formula:

[0068]

[0069] Where R 6 and R 7 Each is independently hydrogen or a monovalent organic group having 1 to 20 carbon atoms;

[0070] R 8 It is a divalent straight-chain alkylene having 1 to 20 carbon atoms, or a divalent branched alkylene having 3 to 20 carbon atoms, each of which may optionally contain one or more heteroatoms within the chain;

[0071] R 9 Each is independently selected from a monovalent group, wherein the monovalent group is selected from a straight-chain alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a cycloalkyl 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.

[0072] R 10 The group is independently selected from monovalent groups, wherein the monovalent group is selected from straight-chain alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, cycloalkyl 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 wherein

[0073] b is an integer with the value 1, 2, or 3.

[0074] In any of the foregoing embodiments, the urea-functionalized organosilicon is represented by the following formula:

[0075] .

[0076] In any of the foregoing embodiments, the compound represented by Formula 1 is present in an amount of about 0.1 to 10% by weight based on the total weight of the composition.

[0077] In any of the foregoing embodiments, the compound of Formula 1 is present in the following amounts: about 0.01 wt% to about 90 wt%, about 0.05 wt% to about 80 wt%, about 0.1 wt% to about 75 wt%, about 0.2 wt% to about 60 wt%, about 0.5 wt% to about 50 wt%, about 1 wt% to about 25 wt%, or about 5 wt% to about 10 wt% based on the total weight of the composition; preferably 1-10 wt%, 10-50 wt%, or 50-90 wt% based on the total weight of the composition.

[0078] In any of the foregoing embodiments, the composition is a solvent-free composition.

[0079] In one aspect, an energy storage device is provided, comprising: (a) at least one electrode; and (b) an electrolyte, wherein the at least one electrode comprises a composition according to any of the foregoing embodiments.

[0080] In one embodiment, the device has a specific capacity of at least 20% of its post-first-cycle specific capacity after at least 500 electrochemical cycles, as determined by a cycle stability study. In any of the preceding embodiments, the device has a specific capacity of at least 40% of its post-first-cycle specific capacity after at least 500 electrochemical cycles, as determined by a cycle stability study. In any of the preceding embodiments, the device has a specific capacity of at least 60% of its post-first-cycle specific capacity after at least 500 electrochemical cycles, as determined by a cycle stability study.

[0081] In any of the foregoing embodiments, the device is a secondary battery pack.

[0082] In any of the foregoing embodiments, the secondary battery pack is a lithium-ion battery pack.

[0083] In another aspect, 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 activator; and (d) an optional binder, wherein the capacity retainer maintains the specific capacity of the electrode in the range of 20-80% of its specific capacity after the first cycle after 500 electrochemical cycles.

[0084] In one embodiment, the capacity-retaining agent is represented by the following formula:

[0085]

[0086] Where R 1' R 2' R 3' R 4' R 5' and R 6' Each independently as R 4 OR 5 or urea functional group, wherein R 4 Independently, it is a straight-chain alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, and an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms.

[0087] R 5 Independently, it is a straight-chain alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a cycloalkyl 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, or an aralkyl group having 7 to 20 carbon atoms.

[0088] a' or b' is an integer having a value in the range of 0-500, provided that at least one of a' or b' is greater than 0; and

[0089] R 1' R 2' R 3' R 4' R 5' and / or R 6' At least one of them is a urea functional group.

[0090] In one embodiment, the urea functional group is represented by the following formula:

[0091]

[0092] Where R 1 and R 2 Each is independently selected from hydrogen and monovalent organic groups having 1 to 20 carbon atoms;

[0093] R 3 It is a divalent straight-chain alkylene having 1 to 20 carbon atoms, or a divalent branched alkylene having 3 to 20 carbon atoms, each of which optionally contains one or more heteroatoms within the chain;

[0094] X is selected from substituted or unsubstituted aromatic groups having 6 to 20 carbon atoms and heterocyclic groups containing 1 to 20 heteroatoms, wherein the aromatic groups and / or heterocyclic groups are optionally substituted with alkyl groups having 1 to 12 carbon atoms, and optionally contain heteroatoms selected from O, N and / or S, and a ureidofunctional group; and

[0095] Z stands for oxygen.

[0096] On the other hand, an electrode is provided, which comprises a composition according to any of the foregoing embodiments.

[0097] In another aspect, an electrochemical cell is provided, comprising a negative electrode and a positive electrode, wherein the negative electrode, the positive electrode, or the negative electrode and the positive electrode comprise the composition according to claims 1-21.

[0098] In one embodiment, the electrochemical cell also includes a separator.

[0099] In any of the foregoing embodiments, the electrochemical cell is a lithium-ion battery pack.

[0100] On the other hand, an energy storage device is provided, comprising: (a) at least one electrode; and (b) an electrolyte, wherein at least one electrode comprises a composition.

[0101] On the other hand, an electrode is provided, which comprises the composition shown and described.

[0102] In another aspect, an electrochemical cell is provided, which includes a negative electrode and a positive electrode, wherein the negative electrode, the positive electrode, or the negative electrode and the positive electrode comprise a composition as shown and described.

[0103] In another aspect, 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-retaining agent; (c) an electrode activator; and (d) an optional binder, wherein the capacity-retaining agent maintains the specific capacity of the electrode in the range of 20-80% of its specific capacity after the first cycle after 500 electrochemical cycles.

[0104] The following figures illustrate various illustrative aspects. Some improvements and novelties are clearly indicated, while others are apparent from the description and figures. Attached Figure Description

[0105] Figure 1 Cyclic voltammetry of a battery using a composition with urea-functionalized organosilicon materials;

[0106] Figure 2 Cyclic voltammetry of a battery using a control binder without urea-functionalized organosilicon materials; and

[0107] Figure 3 The constant current charge / discharge curves are shown for various number of cycles. Detailed Implementation

[0108] Reference will now be made to exemplary embodiments and examples illustrated in the accompanying drawings. It should be understood that other embodiments may be utilized, and structural and functional changes may be made. Furthermore, features of various embodiments may be combined or modified. Therefore, the following description is presented by way of illustration only and should not in any way limit the various alternatives and modifications that may be made to the illustrated embodiments. Numerous specific details in this disclosure provide a thorough understanding of the subject matter. It should be understood that aspects of this disclosure may be practiced, etc., with other embodiments, not necessarily including all aspects described herein.

[0109] As used herein, the terms “example” and “exemplary” mean instance or illustration. The terms “example” or “exemplary” do not indicate key or preferred aspects or implementations. Unless the context otherwise requires, the word “or” is intended to indicate inclusion rather than exclusivity. For example, the phrase “A employs B or C” includes any inclusive permutation (e.g., A employs B; A employs C; or A employs both B and C). Furthermore, unless the context otherwise requires, the article “a” generally means “one or more”.

[0110] This document provides compositions suitable for electrodes, wherein the compositions comprise a polymer resin, a compound, an electrode activator, and optionally a binder. The compound is a urea-functionalized organosilicon material.

[0111] In one embodiment, the urea-functionalized organosilicon material comprises a urea-functionalized silane. In another embodiment, the urea-functionalized organosilicon material comprises a urea-functionalized siloxane. The urea-functionalized organosilicon material is suitable as a binder additive in electrode compositions used to construct electrochemical cells, such as battery packs. The urea-functionalized organosilicon material can be mixed with polymer resins, electrode activators, and binders to form compositions for positive or negative electrodes.

[0112] The composition contains a urea-functionalized organosilicon material as an additive. The urea-functionalized organosilicon can be represented by a compound of formula (I):

[0113] (I)

[0114] Where R 1' R 2' R 3' R 4' R 5' and R 6' Each independently selected from R 4 OR 5 and urea functional groups, wherein R 4 Independently selected from monovalent groups, said monovalent group being selected from straight-chain alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, cycloalkyl 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, which are selected from straight-chain alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, cycloalkyl 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.

[0115] a' or b' is 0-500, provided that at least one of these a' or b' is greater than 0; and R 1' To R 6' At least one of them is a urea functional group. It will be understood that when a' is greater than 0, then b' is 0, and when b' is greater than 0, a' is 0.

[0116] The urea functional group has the following formula:

[0117]

[0118] Where R 1 and R 2 Each is independently selected from hydrogen or a monovalent organic group having 1 to 20 carbon atoms;

[0119] R 3 It is a divalent straight-chain alkylene having 1 to 20 carbon atoms, or a divalent branched alkylene having 3 to 20 carbon atoms, each of which may optionally contain one or more heteroatoms within the chain;

[0120] X is selected from an aromatic group having 6 to 20 carbon atoms, a heterocyclic group containing 5 to 20 heteroatoms, wherein the aromatic group and / or heterocyclic group is optionally substituted with an alkyl group having 1 to 12 carbon atoms, and optionally contains a heteroatom selected from O, N and / or S, or a urea functional group; and

[0121] Z stands for oxygen.

[0122] In one embodiment, the urea-functionalized organosilicon material is a silane of the following formula (b' is 0):

[0123]

[0124] Where R 1' R 3' R 5' and R 6' Each independently selected from R 4 OR 5 and urea functional groups, wherein R 4 The group is independently selected from monovalent groups, which are selected from straight-chain alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, cycloalkyl 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.

[0125] R 5 The group is independently selected from monovalent groups, which are selected from straight-chain alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, cycloalkyl 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.

[0126] a' is 1-500; and

[0127] R 1' R 3' R 5' and R 6' At least one of them is selected from the urea functional group.

[0128] In one implementation, R 6' It has a urea functional group, and R 1' R 3' and R 5' Each independently selected from R 4 and OR 5 .

[0129] In one embodiment, the urea-functionalized organosilicon material is a silane selected from compounds of the following formula:

[0130]

[0131] Where R 1 and R 2 Each is independently selected from hydrogen or a monovalent organic group having 1 to 20 carbon atoms;

[0132] R 3It is a divalent straight-chain alkylene having 1 to 20 carbon atoms, or a divalent branched alkylene having 3 to 20 carbon atoms, each of which may optionally contain one or more heteroatoms within the chain;

[0133] R 4 The group is independently selected from monovalent groups, which are selected from straight-chain alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, cycloalkyl 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.

[0134] R 5 The group is independently selected from monovalent groups, which are selected from straight-chain alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, cycloalkyl 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.

[0135] X is selected from an aromatic group having 6 to 20 carbon atoms, a heterocyclic group containing up to 20 heteroatoms, wherein the aromatic group and / or heterocyclic group is optionally substituted with an alkyl group having 1 to 12 carbon atoms, and optionally contains a heteroatom selected from O, N and / or S, or a urea functional group:

[0136] Z represents oxygen; and a is 1, 2, or 3.

[0137] n is between 1 and 500.

[0138] R 1 and R 2 Each group is independently selected from hydrogen and monovalent groups having 1 to 20 carbon atoms, 2 to 15 carbon atoms, 4 to 12 carbon atoms, or 6 to 10 carbon atoms. Examples of suitable monovalent organic groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc. In one embodiment, R 1 and R 2 Each is independently selected from hydrogen and monovalent groups having 1 to 4 carbon atoms. In one embodiment, R 1 and R 2 Each is hydrogen.

[0139] In the implementation, R 3 Selected from divalent straight-chain 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.

[0140] In the implementation, R 4Independently, it is a monovalent group selected from: straight-chain alkyl groups containing 1 to 8 carbon atoms, 1 to 4 carbon atoms, or 1 to 2 carbon atoms; or branched-chain alkyl groups containing 3 to 8 carbon atoms, 4 to 6 carbon atoms, or 3 to 4 carbon atoms. Suitable R 4 Examples of groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, etc., 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, straight-chain alkyl groups containing 2 to 8 carbon atoms and hydroxyl groups, preferably 2 to 4 carbon atoms and hydroxyl groups, or branched alkyl groups containing 3 or 4 carbon atoms and hydroxyl groups.

[0141] R 5 Independently, it is a monovalent group selected from the following: a straight-chain 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 a phenyl group; or an aralkyl group containing 7 to 10 carbon atoms or 7 to 9 carbon atoms.

[0142] In one embodiment, X is selected from an aromatic group containing 6 carbon atoms, such as a phenyl group, or a heterocyclic group containing 6 atoms and up to 5 heteroatoms. X can be substituted or unsubstituted. X can 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 ureyl 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.

[0143] In one implementation, X is selected from groups of the following formula:

[0144]

[0145] J1, J2, and J3 are each independently a substituted or unsubstituted C or N atom, and the dashed line between J1, J2, and J3 represents an optional double bond between J1 and J2 or between J2 and J3. When any of J1, J2, or J3 is a substituted N atom, the atom does not participate in the double bond.

[0146] Some non-restricted instances of X include:

[0147] ; ; ; ;and

[0148] Where R 11 Selected from hydrogen and monovalent organic groups having 1 to 12 carbon atoms.

[0149] X may be substituted with an alkyl group having 1 to 12 carbon atoms, 2 to 10 carbon atoms, or 4 to 6 carbon atoms, or a urea group. The alkyl group may optionally contain a heteroatom selected from O, N, and / or S. In one embodiment, the X group is substituted with a urea group of the following formula:

[0150]

[0151] Where R 6 and R 7 Each is independently selected from hydrogen or a monovalent organic group having 1 to 20 carbon atoms;

[0152] R 8 It is a divalent straight-chain alkylene having 1 to 20 carbon atoms, or a divalent branched alkylene having 3 to 20 carbon atoms, each of which may optionally contain one or more heteroatoms within the chain;

[0153] R 9 Each is independently selected from a monovalent group, wherein the monovalent group is selected from a straight-chain alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a cycloalkyl 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.

[0154] R 10 Each group is independently selected from monovalent groups, wherein the monovalent group is selected from straight-chain alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, cycloalkyl 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

[0155] b can be 1, 2, or 3.

[0156] R 6 and R 7 Each group is independently selected from hydrogen and monovalent groups having 1 to 20 carbon atoms, 2 to 15 carbon atoms, 4 to 12 carbon atoms, or 6 to 10 carbon atoms. Examples of suitable monovalent organic groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, etc. In one embodiment, R 6 and R 7 Independently selected from hydrogen and monovalent groups having 1 to 4 carbon atoms. In one embodiment, R 6 and R7 Each is hydrogen.

[0157] In the implementation, R 8 Selected from divalent straight-chain 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.

[0158] In the implementation, R 9 Each is independently a monovalent group selected from the following: a straight-chain alkyl group containing 1 to 8 carbon atoms, 1 to 4 carbon atoms, or 1 to 2 carbon atoms; or a branched-chain alkyl group containing 3 to 8 carbon atoms or 3 to 4 carbon atoms. Used for R 9 Examples of suitable groups include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, etc., cycloalkyl containing 6 carbon atoms, alkenyl containing 2 to 8 carbon atoms, preferably 2 to 4 carbon atoms, aryl, such as phenyl, or aralkyl containing 7 to 10 carbon atoms, preferably 7 to 9 carbon atoms, straight-chain alkyl containing 2 to 8 carbon atoms and a hydroxyl group, straight-chain alkyl containing 2 to 4 carbon atoms and a hydroxyl group, or branched alkyl containing 3 or 4 carbon atoms and a hydroxyl group.

[0159] R 10 Independently, it is a monovalent group selected from the following: a straight-chain 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 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 a phenyl group; or an aralkyl group containing 7 to 10 carbon atoms or 7 to 9 carbon atoms.

[0160] In one embodiment of equation (I), R 1 and R 2 Each is represented by H, Z by O, and R by [other symbols]. 3 It is a divalent straight-chain alkylene group containing 2 to 6 carbon atoms, with subscript a of 3, and each R 4 It is a straight-chain alkyl group containing 1 to 3 carbon atoms.

[0161] In another embodiment of formula (I), X is phenyl, and R 1 and R 2 Each is H, Z is O, Z is a divalent straight-chain alkylene group containing 2 to 6 carbon atoms, subscript a is 3, and each R 4 It is a straight-chain alkyl group containing 1 to 3 carbon atoms.

[0162] In another embodiment of formula (I), X is a heterocyclic group containing one or two N atoms, and R 1 and R 2 Each is represented by H, Z by O, and R by [other symbols]. 3It is a divalent straight-chain alkylene group containing 2 to 6 carbon atoms, with subscript a of 3, and each R 4 It is a straight-chain alkyl group containing 1 to 3 carbon atoms.

[0163] In another embodiment of formula (I), X is a heterocyclic group containing two N atoms, and the ring is substituted with an O atom, R 1 and R 2 Each is represented by H, Z by O, and R by [other symbols]. 3 It is a divalent straight-chain alkylene group containing 2 to 6 carbon atoms, with subscript a of 3, and each R 4 It is a straight-chain alkyl group containing 1 to 3 carbon atoms.

[0164] In another embodiment of formula (I), X is a heterocyclic group containing 2 N atoms, wherein the ring is substituted by an O atom in the form of a carbonyl O and an alkyl group containing 1 or 2 carbon atoms, and R 1 and R 2 Each is represented by H, Z by O, and R by [other symbols]. 3 It is a divalent straight-chain alkylene group containing 2 to 6 carbon atoms, with subscript a of 3, and each R 4 It is a straight-chain alkyl group containing 1 to 3 carbon atoms.

[0165] In one embodiment, the urea-functionalized organosilicon is a urea-functionalized silane selected from compounds of the following formula (i.e., compounds of formula 1, wherein a' is greater than 0 and b' is 0):

[0166] (II).

[0167] Some non-limiting examples of suitable urea-functionalized organosilicones include urea-functionalized silanes represented by the following:

[0168]

[0169]

[0170]

[0171]

[0172]

[0173]

[0174] Where R 1 and R 2 Each is independently selected from H and alkyl groups having 1 to 12 carbons, 1 to 6 carbons, or 1 to 4 carbons, and R 3 and R 8As described above, and in the embodiments selected from C1-12 alkylene, C2-C10 alkylene, C3-C8 alkylene, or C4-C6 alkylene. In the embodiments, R 1 and R 2 Each is H, and R 3 and R 8 Each is a C3 alkylene group.

[0175] In one embodiment, the urea-functionalized material is a urea-functionalized polyorganosiloxane of the following formula (i.e., a compound of formula 1, wherein b' is greater than 0 and a' is 0):

[0176] M 1 c M 2 d D 1 e D 2 f T 1 g T 2 h Q i

[0177] in:

[0178] M 1 For (R) 16 (R) 17 (R) 18 SiO 1 / 2

[0179] M 2 For (R) 19 (R) 20 (R) 21 SiO 1 / 2

[0180] D 1 For (R) 22 (R) 23 SiO 2 / 2

[0181] D 2 For (R) 24 (R) 25 SiO 2 / 2

[0182] T 1 For (R) 26 SiO 3 / 2

[0183] T 2 For (R) 27 SiO 3 / 2

[0184] Q is SiO 4 / 2

[0185] R 16 R 17 R 18 R 22 R 23 and R 26 Each independently selected from R 4 and OR 5 ;

[0186] R 19 R 20 R 21 R 24 R 25 and R 27 Each independently selected from R 4 OR 5 and urea functional group, condition is R 19 R 20 R 21 R 24 R 25 and R 27 At least one of them is selected from the urea functional group;

[0187] Where R 4 The group is independently selected from monovalent groups, which are selected from straight-chain alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, cycloalkyl 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.

[0188] R 5 The group is independently selected from monovalent groups, which are selected from straight-chain alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, cycloalkyl 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.

[0189] d, f, and h are each independently greater than 0; and

[0190] c, e, g, and i are each independently 0 or greater.

[0191] The composition comprises a polymer resin. The polymer resin includes, but is not limited to, resin polymers such as polyethylene, polypropylene, polyethylene terephthalate, polymethyl methacrylate, aromatic polyamides, chitosan, alginate, polyacrylic acid, polyimide, cellulose, and nitrocellulose; rubbery polymers such as SBR (styrene-butadiene rubber), isoprene rubber, butadiene rubber, fluorinated elastomers, NBR (acrylonitrile-butadiene rubber), and ethylene-propylene rubber; styrene-butadiene-styrene block copolymers and their hydrogenation products; and thermoplastic elastomer polymers, such as… EPDM (ethylene-propylene-diene terpolymer), styrene-ethylene-butadiene-styrene copolymer, and styrene-isoprene-styrene block copolymer and their hydrogenated products; soft resin polymers, such as syndiotactic 1,2-polybutadiene, polyvinyl acetate, ethylene-vinyl acetate copolymer, and propylene-α-olefin copolymer; fluorinated polymers, such as polyvinylidene fluoride, polytetrafluoroethylene, vinylidene fluoride copolymer, and tetrafluoroethylene-ethylene copolymer; and polymer compositions having ion 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, and when using a combination of resins, the resins can be used in any proportion for a specific application.

[0192] The composition optionally includes a binder. Examples of optional binders include, but are not limited to, carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, oxidized starch, monostarch phosphate, casein, polyvinylpyrrolidone, and salts thereof. Optional binders may be provided as a single material or as a combination of two or more thickeners.

[0193] The composition comprises a polymeric 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 polymeric resin in an amount of up to about 10% by weight based on the total weight of the electrode composition. In another embodiment, the electrode composition comprises a polymeric resin in an amount of up to about 4% by weight based on the total weight of the electrode composition.

[0194] In an embodiment, the composition comprises the following amounts of urea-functionalized organosilicon: about 0.01 wt% to about 90 wt%, about 0.05 wt% to about 80 wt%, about 0.1 wt% to about 75 wt%, about 0.2 wt% to about 60 wt%, about 0.5 wt% to about 50 wt%, about 1 wt% to about 25 wt%, or about 5 wt% to about 10 wt%, based on the total weight of the composition.

[0195] The composition may further comprise an electrode activator, wherein the electrode activator is selected from intercalating agents and conductive agents. Intercalating agents are 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, and SiO2. v (0 < v ≦ 2), LiSiO, Sn, SnSiO3, LiSnO and Mg2Sn, SnO w (0 < w ≦ 2). In one or more embodiments, the conductive agent is a carbonaceous conductive agent selected from graphite, including natural graphite and artificial graphite; carbon black, including acetylene black, Ketjen black, channel black, furnace black, lamp black, and thermal cracking black; amorphous carbon, including needle coke; carbon nanotubes; fullerenes; and vapor-grown carbon fibers (VGCF). The composition may contain a single type of conductive agent or two or more conductive agents. The electrode activator is typically used in amounts of about 0.01% by mass or higher, about 0.1% by mass or higher, about 1% by mass or higher, and typically about 50% by mass or lower, about 30% by mass or lower, more preferably about 15% by mass or lower. Amounts of conductive agent below the above ranges result in insufficient conductivity. In contrast, amounts of conductive agent above the above ranges result in low battery pack capacity.

[0196] Unexpectedly, urea-functionalized silicone materials have been found to provide excellent capacity retention for electrode materials over a large number of charge cycles (i.e., charge / discharge cycles). This was observed at both constant current densities and varying rates. Materials with urea-functionalized silicone materials also exhibit excellent capacity recovery after reversing the current density. These materials also exhibit low impedance during cycling. Urea-functionalized silicone materials also enhance the adhesion properties of the electrode materials.

[0197] The composition may be provided as a slurry in combination with a solvent, or as a "dry" solvent-free material. The solvent used to form the slurry may be any solvent capable of dissolving or dispersing the electrode active material, conductive material, and binder therein, as well as any thickeners that may be used. The solvent may be 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 include, but are not limited to, aliphatic hydrocarbons such as hexane; aromatic hydrocarbons such as benzene, toluene, xylene, and methylnaphthalene; heterocyclic compounds such as quinoline and pyridine; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; esters such as methyl acetate and methyl acrylate; amines such as diethylenetriamine and N,N-dimethylaminopropylamine; ethers such as diethyl ether, propylene oxide, and tetrahydrofuran (THF); amides such as N-methylpyrrolidone (NMP), dimethylformamide, and dimethylacetamide; and aprotic polar solvents such as hexamethylphosphoramide and dimethyl sulfoxide.

[0198] The composition is suitable for use in electrochemical devices, such as, for example, battery packs, supercapacitors, fuel cells, and hydrogen storage devices. The electrode composition can be used as part of a positive or negative electrode material. Electrode materials typically include electrode active materials, such as positive or negative electrode active materials suitable for the desired electrode, binder compositions, and current collectors.

[0199] Compositions having urea-functionalized organosilicon groups have been found to provide large capacity retention over a relatively large number of electrochemical cycles. In one embodiment, the electrode composition retains at least 20% of its initial capacity in the energy storage device over at least 500 electrochemical cycles. In another embodiment, the electrode composition retains at least 40% of its initial capacity in the energy storage device over at least 500 electrochemical cycles. In one embodiment, the binder retains at least 60% of its initial capacity in the energy storage device over at least 500 electrochemical cycles.

[0200] The composition comprises electrode active materials, wherein the electrode active materials include positive and / or negative electrode active materials. The positive electrode active material can be any material capable of electrochemically occluding and releasing lithium ions. Examples of positive electrode active materials include, but are not limited to, lithium-containing transition metal complex oxides, lithium-containing transition metal phosphate compounds, sulfur-based materials, and conductive polymers. Particularly suitable positive electrode active materials are lithium-containing transition metal complex oxides and lithium-containing transition metal phosphate compounds. An exemplary positive electrode active material is a lithium-containing transition metal complex oxide that generates a high voltage.

[0201] The transition metal in lithium-containing transition metal composite oxides can be selected from V, Ti, Cr, Mn, Fe, Co, Ni, Cu, etc. Specific examples include lithium-cobalt composite oxides, such as LiCoO2; lithium-nickel composite oxides, such as LiNiO2; lithium-manganese composite oxides, such as LiMnO2, LiMn2O4, and Li2MnO4; and those obtained by substituting the major transition metal atom of these lithium transition metal composite oxides with another element such as 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, LiNi 0.85 Co 0.10 Al 0.05 O2, LiNi 0.5 Co 0.2 Mn 0.3 O2, LiNi 0.6 Co 0.2 Mn 0.2 O2, LiNi 0.33 Co 0.33 Mn 0.33 O2, LiNi 0.8 Co 0.1 Mn 0.1 O2, LiNi 0.45 Co 0.10 Al 0.45 O2, LiMn 1.8 Al 0.2 O4 and LiMn 1.5 Ni 0.5 O4.

[0202] Particularly suitable lithium-containing transition metal composite oxides include LiMn 1.5 Ni 0.5 O4, LiNi 0.5 Co 0.2 Mn 0.3 O2 and LiNi 0.6 Co 0.2 Mn 0.2 O2, each possesses high energy density even at high voltages. LiMn, at voltages of 4.4 V or higher, exhibits... 1.5 Ni 0.5 O4 is preferred. LiNi is used to provide high-capacity lithium-ion secondary battery packs. 0.6 Co 0.2 Mn 0.2 O2, LiNi 0.8 Co0.1 Mn 0.1 O2 and LiNi 0.85 Co 0.10 Al 0.05 Lithium-containing transition metal complex oxides of O2 are particularly suitable.

[0203] The transition metal in lithium transition metal phosphate compounds can be selected from V, Ti, Cr, Mn, Fe, Co, Ni, Cu, etc. Specific examples include iron phosphate, such as LiFePO4, Li3Fe2(PO4)3 and LiFeP2O7, cobalt phosphate, such as LiCoPO4, and those obtained by substituting some of the transition metal atoms that are the main components of these lithium transition metal phosphate compounds with another element such as Al, Ti, V, Cr, Mn, Fe, Co, Li, Ni, Cu, Zn, Mg, Ga, Zr, Nb or Si.

[0204] Examples of lithium-containing transition metal composite oxides include lithium-manganese spinel composite oxides represented by the following formula: Li a Mn 2-b M 1 b O4 (where 0.9 ≦ a; 0 ≦ b ≦ 1.5; and M 1 A lithium-nickel composite oxide represented by the following formula (where at least one metal selected from Fe, Co, Ni, Cu, Zn, Al, Sn, Cr, V, Ti, Mg, Ca, Sr, B, Ga, In, Si, and Ge is used): LiNi 1- c M 2 c O2 (where 0 ≦ c ≦ 0.5; and M 2 Lithium-cobalt composite oxide (LiCo) is selected from at least one metal (Fe, Co, Mn, Cu, Zn, Al, Sn, Cr, V, Ti, Mg, Ca, Sr, B, Ga, In, Si, and Ge) and represented by the following formula: LiCo 1-d M 3 d O2 (where 0 ≦ d ≦ 0.5; and M 3 It is at least one metal selected from Fe, Ni, Mn, Cu, Zn, Al, Sn, Cr, V, Ti, Mg, Ca, Sr, B, Ga, In, Si, and Ge.

[0205] To provide high-power lithium-ion secondary battery packs with high energy density, exemplary positive electrode active materials include LiCoO2, LiMnO2, LiNiO2, LiMn2O4, and LiNi. 0.8 Co 0.15 Al 0.05O2 or LiNi 1 / 3 Co 1 / 3 Mn 1 / 3 O2.

[0206] Other examples of positive electrode active materials include LiFePO4 and LiNi. .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.

[0207] Examples of sulfur-based materials include materials containing sulfur atoms, such as, for example, elemental sulfur, metal sulfides, and organosulfur compounds. Metal sulfides can be metal polysulfides. Organosulfur compounds can be organic polysulfides.

[0208] Examples of metal sulfides include those made of LiS x Compounds represented by (0 < x ≦ 8), derived from Li₂S x Compounds represented by (0 < x ≦8), compounds with 2D layered structures such as TiS2 and MoS2, and chevrel compounds with strong 3D framework structures, such as those represented by the following formula: Me x Mo6S8 (where Me is a transition metal, such as Pb, Ag or Cu).

[0209] Examples of organosulfur compounds include carbon disulfide compounds.

[0210] Organic sulfur compounds can each be loaded onto porous materials such as carbon, and thus used as carbon composite materials. To provide significantly 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 higher, 30% by mass or higher, 40% by mass or higher, and in some embodiments, 85% by mass or lower. 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.

[0211] Examples of conductive polymers include p-doped and n-doped conductive polymers. Examples of conductive polymers also include polyacetylene polymers, polyphenylene polymers, heterocyclic polymers, ionic polymers, ladder polymers, and network polymers.

[0212] To improve continuous charging characteristics, the positive electrode active material may contain lithium phosphate. Lithium phosphate can be used in any manner and can be mixed with the positive electrode active material. The lower limit of the amount of lithium phosphate used relative to the total amount of the positive electrode active material and lithium phosphate is typically 0.1% by mass or higher, 0.3% by mass or higher, or 0.5% by mass or higher. The upper limit is typically 10% by mass or lower, 8% by mass or lower, or 5% by mass or lower.

[0213] Substances having a different composition from the positive electrode active material can be attached to the surface of the positive electrode active material. Examples of substances that can be 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.

[0214] Such substances can adhere to the surface of the positive electrode active material by, for example, the following methods: dissolving or suspending the substance in a solvent, impregnating the solution or suspension into the positive electrode active material, and drying the impregnated material; dissolving or suspending a precursor of the substance in a solvent, impregnating the solution or suspension into the positive electrode active material, and heating the material and the precursor to induce a reaction therebetween; or adding the substance to a precursor of the positive electrode active material and simultaneously sintering the material. In the case of carbon adhesion, for example, carbonaceous materials in the form of activated carbon can subsequently be mechanically adhered to the surface.

[0215] The mass of the material adhering to the surface relative to the positive electrode active material is typically 0.1 ppm or higher, 1 ppm or higher, or 10 ppm or higher, with upper limits typically ranging from 20% or lower, 10% or lower, or 5% or lower. This surface-adhering material reduces oxidation of the electrolyte solution on the positive electrode active material surface, improving battery life. Too little material may not provide sufficient effect. Too much material can hinder the entry and exit of lithium ions, increasing resistance.

[0216] The particles of the positive electrode active material can have any conventionally used shape, such as block shape, polyhedral shape, spherical shape, ellipsoidal shape, plate shape, needle shape, or columnar shape. Primary particles can aggregate to form secondary particles.

[0217] The positive electrode active material can typically have a concentration of 1.5 g / cm³. 3 Or higher, 2.0 g / cm 3 or higher, 2.5 g / cm 3 Or higher, or 3.0 g / cm³ 3Or even higher tap densities. Positive electrode active materials with tap densities below the lower limit lead to an increase in the amount of dispersion medium required to form the positive electrode active material layer, as well as an increase in the amount of conductive material and binder required. Furthermore, the packing fraction of the positive electrode active material in the positive electrode active material layer is limited, resulting in a limitation on the battery pack capacity. Metal composite oxide powders with high tap densities can form positive electrode active material layers with high density. Tap density is generally preferred to be as high as possible, with no upper limit.

[0218] In this disclosure, tap density is defined as the powder filling density (taper density) in g / cm³ when 5 to 10 g of positive electrode active material powder is filled into a 10-ml glass graduated cylinder and the cylinder is tapped 200 times with a stroke of about 20 mm. 3 .

[0219] The particles of the positive electrode active material may have a median particle size d50 of 0.3 μm or larger, 0.5 μm or larger, 0.8 μm or larger, or 1.0 μm or larger (or the secondary particle size when primary particles agglomerate to form secondary particles), with an upper limit of 30 μm or smaller, 27 μm or smaller, 25 μm or smaller, or 22 μm or smaller. Particles with a median particle size below the lower limit may not provide a product with a high tap density. Particles with a median particle size above the upper limit will result in prolonged lithium diffusion within the particles, impairing battery pack performance and producing streaks when forming the positive electrode for the battery pack, i.e., for example when active materials and components such as conductive materials and additives are made into a slurry by adding solvents and the slurry is applied in the form of a film. Mixing two or more positive electrode active materials with different median particle sizes d50 can further improve the ease of filling during positive electrode formation.

[0220] In this disclosure, the median particle size d50 was determined using a known laser diffraction / scattering particle size distribution analyzer. When using an LA-920 (Horiba Ltd.) as the particle size distribution analyzer, the dispersion medium used in the measurement was a 0.1% by mass aqueous solution of sodium hexametaphosphate, and the refractive index was set to 1.24 after 5 minutes of ultrasonic dispersion.

[0221] When primary particles agglomerate to form secondary particles, the average primary particle size of the positive electrode active material can be 0.05 μm or larger, 0.1 μm or larger, or 0.2 μm or larger. The upper limit for such agglomerates can be 5 μm or smaller, 4 μm or smaller, 3 μm or smaller, or 2 μm or smaller. Primary particles with an average primary particle size greater than this upper limit are difficult to form spherical secondary particles, adversely affecting powder filling. Furthermore, such primary particles can have a significantly reduced specific surface area, highly likely to impair battery pack performance, such as output characteristics. In contrast, primary particles with an average primary particle size below this lower limit are typically inadequately grown crystals, leading to, for example, poor charge and discharge reversibility.

[0222] In this disclosure, the primary particle size is measured by scanning electron microscopy (SEM). Specifically, the primary particle size is determined as follows: First, a photograph at 10000x magnification is taken. Fifty arbitrary primary particles are selected, and the maximum length between the left and right boundary lines of each primary particle is measured along a horizontal line. Then, the average of the maximum lengths is calculated, which is defined as the primary particle size.

[0223] The positive electrode active material can preferably have a diameter of 0.1 μm. 2 / g or greater, 0.2 m 2 / g or greater, or 0.3 m 2 BET specific surface area of ​​ / g or greater. Upper limit: 50 m². 2 / g or less, 40 m 2 / g or less, or 30 m 2 / g or less. Positive electrode active materials with a BET specific surface area smaller than the above range can easily impair battery pack performance. Positive electrode active materials with a BET specific surface area larger than the above range are less likely to have an improved tap density, which can lead to difficulties in applying the material when forming the positive electrode active material layer.

[0224] In this disclosure, the BET specific surface area is defined by a surface area analyzer (e.g., a fully automated surface area measuring device, Ohkura Riken Ltd.) determined by single-point BET nitrogen adsorption using a gas flow method, with the sample pre-dried in a nitrogen gas flow at 150°C for 30 minutes and the nitrogen pressure of the nitrogen-helium gas mixture accurately adjusted to 0.3 relative to atmospheric pressure.

[0225] When the lithium-ion secondary battery pack of this disclosure is used as a large lithium-ion secondary battery pack for hybrid vehicles or distributed power generation, it needs to achieve high output. Therefore, the positive electrode active material particles are preferably mainly composed of secondary particles.

[0226] The positive electrode active material particles may contain 0.5 to 7.0 vol% fine particles with an average secondary particle size of 40 μm or less and an average primary particle size of 1 μm or less. The presence of fine particles with an average primary particle size of 1 μm or less increases the contact area with the electrolyte solution and allows lithium ions to diffuse more rapidly between the electrode and the electrolyte solution, improving the output performance of the battery pack.

[0227] Positive electrode active materials can be produced using any conventional method for producing inorganic compounds. In particular, spherical or ellipsoidal active materials can be produced by a variety of methods. For example, a transition metal precursor is dissolved or pulverized and dispersed in a solvent such as water, and the pH of the solution or dispersion is adjusted under stirring to form a spherical precursor. The precursor is recovered and, if necessary, dried. A Li source, such as LiOH, Li₂CO₃, or LiNO₃, is then added, and the mixture is sintered at a high temperature, thereby providing the active material.

[0228] In the production of the positive electrode, one of the above-mentioned positive electrode active materials can be used alone, or two or more materials with different compositions can be used in any combination and proportion. Non-limiting examples of combinations include LiCoO2 and LiMn2O4 (where a portion of the Mn can optionally be replaced by different transition metals (e.g., LiNi)). 0.33 Co 0.33 Mn 0.33 O2), and combinations thereof with LiCoO2 (in which some Co may optionally be replaced by different transition metals).

[0229] To achieve high battery pack capacity, the amount of 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 positive electrode active material in the positive electrode active material layer can be 80% by mass or higher, 82% by mass or higher, or 84% by mass or higher, with an upper limit of 99% by mass or lower, or 98% by mass or lower. Too little positive electrode active material in the positive electrode active material layer will result in insufficient capacity. Conversely, too much will result in insufficient positive electrode strength.

[0230] The negative electrode consists of a negative electrode active material layer containing negative electrode active material and a current collector.

[0231] The negative electrode material can be any material capable of electrochemically absorbing and releasing lithium ions. Specific examples include carbon materials, alloyed materials, lithium-containing metal composite oxide materials, and conductive polymers. One of these can be used alone, or two or more of them can be used in any combination.

[0232] Examples of negative electrode active materials include carbonaceous materials that can absorb and release lithium, such as pyrolysis products of organic matter under various pyrolysis conditions, artificial graphite, and natural graphite; metal oxide materials that can absorb and release 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 can be used in combination.

[0233] The carbonaceous material capable of absorbing and releasing lithium is preferably artificial graphite produced by high-temperature treatment of easily graphitizable pitch from various raw materials, purified natural graphite, or material obtained by surface-treating such graphite with pitch or other organic substances and subsequently carbonizing the surface-treated graphite. To achieve a good balance between initial irreversible capacity and high current density charging and discharging characteristics, the carbonaceous material is more preferably selected from: carbonaceous materials obtained by heat-treating natural graphite, artificial graphite, artificial carbonaceous material, or artificial graphitic material at 400°C to 3200°C once or more; carbonaceous materials that allow the negative electrode active material layer to contain at least two or more carbonaceous materials with different crystallinities and / or have interfaces between carbonaceous materials with different crystallinities; and carbonaceous materials that allow the negative electrode active material layer to have interfaces between at least two or more carbonaceous materials with different orientations. One of these carbonaceous materials can be used alone, or two or more of them can be used in any combination and proportion.

[0234] Examples of carbonaceous materials obtained by heat-treating artificial carbonaceous or artificial graphite materials once or more at 400°C to 3200°C include coal-based coke, petroleum-based coke, coal-based pitch, petroleum-based pitch, and those prepared by oxidizing these pitches; needle coke, pitch coke, and carbonaceous materials prepared by partially graphitizing these cokes; pyrolysis products of organic materials such as furnace black, acetylene black, and pitch-based carbon fibers; carbonizable organic materials and their carbides; and solutions prepared by dissolving carbonizable organic materials in low molecular weight organic solvents such as benzene, toluene, xylene, quinoline, or n-hexane, and their carbides.

[0235] The metallic material used as the negative electrode active material (excluding lithium-titanium composite oxides) can be any compound capable of absorbing and releasing lithium, and examples include elemental lithium, elemental metals and alloys constituting lithium alloys, and their oxides, carbides, nitrides, silicides, sulfides, and phosphides. The elemental metals and alloys constituting lithium alloys are preferably materials containing any metallic and half-metallic elements from Groups 13 and 14, more preferably elemental metals of 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 of them may be used in any proportion.

[0236] Examples of negative electrode active materials containing at least one atom selected from a specific metallic element include elemental metals of any one specific metallic element, alloys of two or more specific metallic elements, alloys of one or more specific metallic elements with one or more other metallic elements, compounds containing one or more specific metallic elements, and complex compounds of compounds, such as oxides, carbides, nitrides, silicides, sulfides, and phosphides. Such elemental metals, alloys, or metallic compounds used as negative electrode active materials can yield high-capacity battery packs.

[0237] Further examples include compounds in which any of the aforementioned composite compounds are bonded to several elements, such as elemental metals, alloys, and nonmetallic elements. Specifically, in the case of silicon or tin, for example, an alloy of that element with a metal that does not act as a negative electrode can be used. In the case of tin, for example, a composite compound comprising a combination of five or six elements, including tin, a metal that acts as a negative electrode (excluding silicon), a metal that does not act as a negative electrode, and a nonmetallic element, can be used.

[0238] Specific examples of negative electrode active materials include elemental Si, SiB4, SiB6, Mg2Si, Ni2Si, TiSi2, MoSi2, CoSi2, NiSi2, CaSi2, CrSi2, Cu6Si, FeSi2, MnSi2, NbSi2, TaSi2, VSi2, WSi2, ZnSi2, SiC, Si3N4, Si2N2O, and SiO2. v (0 < v ≦ 2), LiSiO, elemental tin, SnSiO3, LiSnO, Mg2Sn and SnO w (0 < w ≦ 2).

[0239] Examples further include Si or Sn as the first component, and a composite material of the second and third components. The second component is, for example, at least one selected from cobalt, iron, magnesium, titanium, vanadium, chromium, manganese, nickel, copper, zinc, gallium, and zirconium. The third component is, for example, at least one selected from boron, carbon, aluminum, and phosphorus.

[0240] To achieve high battery pack capacity and excellent battery pack characteristics, the preferred metal material is elemental silicon or tin (which may contain trace impurities), SiO2. v (0 < v ≦ 2), SnO w (0 ≦ w ≦ 2), Si-Co-C composite material, Si-Ni-C composite material, Sn-Co-C composite material or Sn-Ni-C composite material.

[0241] Lithium-containing metal composite oxide materials used as negative electrode active materials can be any material capable of absorbing and releasing lithium. Materials containing titanium and lithium are preferred for achieving good high current density charge and discharge characteristics, lithium-containing metal composite oxide materials containing titanium are more preferred, and lithium-titanium composite oxides (hereinafter abbreviated as "lithium-titanium composite oxides") are still more preferred. In other words, the use of spinel-structured lithium-titanium composite oxides in the negative electrode active material for electrolyte battery packs is particularly preferred because it significantly reduces output resistance.

[0242] Examples of lithium-titanium composite oxides include compounds represented by the following formula:

[0243] Li x Ti y M z O4

[0244] M is at least one element selected from Na, K, Co, Al, Fe, Ti, Mg, Cr, Ga, Cu, Zn, and Nb.

[0245] To achieve a good balance in battery pack performance, the components described above are particularly suitable if they meet any of the following conditions:

[0246] (i) 1.2 ≦ x ≦ 1.4, 1.5 ≦ y ≦ 1.7, z = 0

[0247] (ii) 0.9 ≦ x ≦ 1.1, 1.9 ≦ y ≦ 2.1, z = 0

[0248] (iii) 0.7 ≦ x ≦ 0.9, 2.1 ≦ y ≦ 2.3, z = 0.

[0249] A particularly suitable compound composition is Li corresponding to composition (i). 4 / 3 Ti 5 / 3 O4, corresponding to Li1Ti2O4 in composition (ii), and Li corresponding to composition (iii) 4 / 5 Ti 11 / 5 O4. Examples of structures satisfying Z ≠ 0 include Li. 4 / 3 Ti 4 / 3 Al 1 / 3O4.

[0250] The battery pack may use an electrolyte solution. The electrolyte solution is not particularly limited and can be selected according to the desired specific application or intended use. The electrolyte solution may contain an electrolyte salt and a solvent. For lithium battery packs, the electrolyte salt is selected from lithium salts. Examples of lithium salts include, but are not limited to, inorganic lithium salts such as LiPF6, LiBF4, LiClO4, LiAlF4, LiSbF6, LiTaF6, LiWF7, LiAsF6, LiAlCl4, LiI, LiBr, LiCl, and LiB. 10 Cl 10 Lithium salts containing S=O groups include: Li₂SiF₆, Li₂PFO₃, and LiPO₂F₂; lithium tungstate, such as LiWOF₅; lithium carboxylate, such as HCO₂Li, CH₃CO₂Li, CH₂FCO₂Li, CHF₂CO₂Li, CF₃CO₂Li, CF₃CH₂CO₂Li, CF₃CF₂CO₂Li, CF₃CF₂CF₂CO₂Li, and CF₃CF₂CF₂CF₂CO₂Li; lithium salts containing S=O groups, such as FSO₃Li, CH₃SO₃Li, CH₂FSO₃Li, CHF₂SO₃Li, CF₃SO₃Li, CF₃CF₂SO₃Li, CF₃CF₂CF₂SO₃Li, lithium methylsulfate, and lithium ethylsulfate (C₂H₅OSO₃Li). and 2,2,2-trifluoroethyl lithium sulfate; lithium imide salts, such as LiN(FCO)2, LiN(FCO)(FSO2), LiN(FSO2)2, LiN(FSO2)(CF3SO2), LiN(CF3SO2)2, LiN(C2F5SO2)2, bisperfluoroethanesulfonyl imide lithium, cyclic 1,2-perfluoroethanedisulfonyl imide lithium, cyclic 1,3-perfluoropropanedisulfonyl imide lithium, cyclic 1,2-ethanedisulfonyl imide lithium, cyclic 1,3-propanedisulfonyl imide lithium, cyclic 1,4-perfluorobutanedisulfonyl imide lithium, LiN(CF3SO2)(FSO2), LiN(CF3SO2)(C3F7SO2), LiN(CF3SO2)(C4F9SO2) and LiN(POF2)2; methyl lithium (lithium methide) salts, such as LiC(FSO2)3, LiC(CF3SO2)3 and LiC(C2F5SO2)3; and fluorine-containing organolithium salts, such as salts represented by the following formula: LiPF6 a (C n F 2n+1 ) 6-a(Where a is an integer from 0 to 5; and n is an integer from 1 to 6), for example, 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, as well as 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).

[0251] The solvent can be any of a variety of non-aqueous, aprotic, and polar organic compounds. Typically, solvents can be carbonates, carboxylic esters, ethers, lactones, sulfones, phosphate esters, nitriles, and ionic liquids. Carbonate solvents useful herein include, but are not limited to: cyclic carbonates, such as propylene carbonate and butenyl carbonate, and linear carbonates, such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, and ethyl propyl carbonate.

[0252] Useful carboxylic acid ester 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.

[0253] 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.

[0254] 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.

[0255] Useful phosphate esters include, but are not limited to: trimethyl phosphate, triethyl phosphate, tri(2-chloroethyl) phosphate, tri(2,2,2-trifluoroethyl) phosphate, tripropyl phosphate, triisopropyl phosphate, tributyl phosphate, trihexyl phosphate, triphenyl phosphate, tricresyl phosphate, methyl vinyl phosphate, and ethyl vinyl phosphate.

[0256] Useful sulfones include, but are not limited to: nonfluorinated 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 perfluorinated sulfones, such as di(trifluoromethyl) sulfone, di(pentafluoroethyl) sulfone, trifluoromethyl pentafluoroethyl sulfone, trifluoromethyl nonafluorobutyl sulfone and pentafluoroethyl nonafluorobutyl sulfone.

[0257] Useful nitrile materials include, but are not limited to: acetonitrile, propionitrile, butyronitrile, and dinitrile, CN[CH2] n CN has various alkane chain lengths (n=1-8).

[0258] Ionic liquids (ILs) are salts in a liquid state. In some contexts, the term has been limited to salts with melting points below an arbitrary temperature, such as 100°C (212°F). ILs are primarily composed of ions and short-lived ion pairs. Common anions of ILs are TFSi, FSi, BOB, and PF. 6-x R x Ionic liquids include, but are not limited to, ionic liquids based on the bis(oxalate)borate (BOB) anion, such as N-cyanoethyl-N-methylpyrrolidone BOB, 1-methyl-1-(2-methylsulfinylethyl)-pyrrolidone BOB, and 1-methyl-1-((1,3,2-dioxothiacyclopentane-2-oxide-4-yl)methyl)pyrrolidone BOB; and ionic liquids based on the tris(pentafluoroethyl)trifluorophosphate (FAP) anion, such as N-allyl-N-methylpyrrolidone FAP, N-(ethylene oxide-2-ylmethyl)N-methylpyrrolidone FAP, and N- (Prop-2-ynyl)N-methylpyrrolidineonium FAP; ionic liquids based on the bis(trifluoromethanesulfonyl)imine (TFSI) anion, such as N-propyl-N-methylpyrrolidineonium TFSI, 1,2-dimethyl-3-propylimidazolium TFSI, 1-octyl-3-methylimidazolium TFSI and 1-butyl-methylpyrrolidineonium TFSI; ionic liquids based on the bis(fluorosulfonyl)imine (FSI) anion, such as N-butyl-N-methylmorpholinium FSI and N-propyl-N-methylpiperidinium FSI; and other ionic liquids, such as 1-ethyl-3-methylimidazolium tetrafluoroborate.

[0259] Two or more of these solvents can be used in the electrolyte solution. Other solvents may be used, provided they are non-aqueous and aprotic and capable of dissolving the salt, such as N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, and N,N-dimethyltrifluoroacetamide. Carbonates are preferred, with ethylene carbonate (EC), ethyl methyl carbonate (EMC), and mixtures thereof being most preferred. The amount of solvent is 70% to 95% of the total electrolyte weight, more preferably, the amount of salt is 80% to 90% of the total electrolyte weight.

[0260] Examples of electrochemical devices include lithium-ion secondary battery packs, lithium-ion capacitors, capacitors such as hybrid capacitors and electric double-layer capacitors, radical battery packs, solar cells, particularly dye-sensitized solar cells, lithium-ion primary battery packs, fuel cells, various electrochemical sensors, electrochromic elements, electrochemical switching elements, aluminum electrolytic capacitors, and tantalum electrolytic capacitors. Lithium-ion secondary battery packs, lithium-ion capacitors, and electric double-layer capacitors are preferred. Modules incorporating electrochemical devices are also an aspect of this disclosure.

[0261] The lithium-ion secondary battery pack may further include a separator. The separator can be formed of any known material and can have any known shape, provided that the resulting separator is stable to the electrolyte solution and has excellent liquid retention capabilities. The separator is preferably in the form of a porous sheet or nonwoven fabric, formed of a material stable to the electrolyte solution of this disclosure, such as resin, glass fiber, or inorganic materials, and has excellent liquid retention capabilities.

[0262] Examples of materials for resin or glass fiber separators include polyolefins such as polyethylene and polypropylene, aramids, polytetrafluoroethylene, polyethersulfone, and glass filters. One of these materials can be used alone, or two or more can be combined in any proportion, for example, in the form of a polypropylene / polyethylene bilayer membrane or a polypropylene / polyethylene / polypropylene trilayer membrane. To achieve good permeability of the electrolyte solution and good sealing effect, the separator is preferably a porous sheet or nonwoven fabric formed of polyolefins such as polyethylene or polypropylene.

[0263] Separators can have any thickness, typically 1 μm or greater, 5 μm or greater, or 8 μm or greater, and typically 50 μm or less, 40 μm or less, or 30 μm or less. Separators thinner than these ranges can have poor insulation and mechanical strength. Separators thicker than these ranges result not only in poor battery pack performance, such as poor rate characteristics, but also in low energy density of the overall electrolyte battery pack.

[0264] Porous separators, such as porous sheets or nonwoven fabrics, can have any porosity. Porosity is typically 20% or higher, preferably 35% or higher, more preferably 45% or higher, and typically 90% or lower, preferably 85% or lower, more preferably 75% or lower. Separators with porosities below these ranges tend to have high film resistivity, resulting in poor rate performance. Separators with porosities above these ranges tend to have low mechanical strength, resulting in poor insulation.

[0265] The separator can also have any average pore size. The average pore size is typically 0.5 μm or smaller, or 0.2 μm or smaller, and typically 0.05 μm or larger. Separators with an average pore size larger than the above range can easily lead to short circuits. Separators with an average pore size smaller than the above range can have high film resistivity, resulting in poor rate performance.

[0266] Examples of inorganic materials include oxides such as aluminum oxide and silicon dioxide, nitrides such as aluminum nitride and silicon nitride, and sulfates such as barium sulfate and calcium sulfate, each in the form of particles or fibers.

[0267] The separator is in the form of a thin film, such as a nonwoven fabric, woven cloth, or microporous membrane. The film advantageously has a pore size of 0.01 to 1 μm and a thickness of 5 to 50 μm. Instead of the aforementioned separate films, the separator may have a structure in which a composite porous layer containing the aforementioned inorganic particles is disposed on the surface of one or both of the positive and negative electrodes, using a resin binder. For example, a fluorinated resin with 90% alumina particles having a particle size of less than 1 μm can be used as a binder to be applied to the corresponding surface of the positive electrode to form a porous layer.

[0268] <Battery Pack Design>

[0269] The electrode assembly can be a laminated structure comprising the aforementioned positive and negative electrode plates with the aforementioned separator between them, or a wound structure comprising the aforementioned positive and negative electrode plates in a spiral shape with the aforementioned separator between them. The proportion of the electrode assembly volume in the internal volume of the battery pack (hereinafter referred to as the electrode assembly proportion) is typically 40% or higher, or 50% or higher, and typically 90% or lower, or 80% or lower.

[0270] In an electrode assembly with a laminated structure, the metal core portion of the corresponding electrode layer is preferably bundled and soldered to the terminals. If the electrode has a large area, the internal resistance is high. Therefore, multiple terminals can preferably be arranged in the electrode to reduce resistance. In an electrode assembly with a wound structure, multiple lead structures can be arranged on each of the positive and negative electrodes and bundled to the terminals. This reduces internal resistance.

[0271] The outer casing can be made of any material that is stable to the electrolyte solution to be used. Specific examples include metals such as nickel-plated steel, stainless steel, aluminum and aluminum alloys, and magnesium alloys, and laminates of resin and aluminum foil. Metals such as aluminum or aluminum alloys or laminates are advantageously used to reduce weight.

[0272] The outer casing made of metal can have a sealing structure formed by welding the metal using laser welding, resistance welding, or ultrasonic welding, or a gap-filling structure using metal with resin gaskets in between. The outer casing made of laminate can have a sealing structure formed by hot-melt resin layers. To improve sealing, a resin different from the laminate resin can be disposed between the resin layers. In particular, in the case of forming a sealing structure by hot-melt resin layers with current collectors in between, the metal and resin will be bonded together. Therefore, the resin disposed between the resin layers is advantageously a resin having polar groups or a modified resin having polar groups introduced therein.

[0273] The lithium-ion secondary battery pack disclosed herein can have any shape, such as cylindrical, square, laminated, coin-shaped, or large. The shape and structure of the positive electrode, negative electrode, and separator can be changed according to the shape of the battery pack.

[0274] Example

[0275] Electrode fabrication for lithium-ion coin cells (button cells) comprises a negative electrode active material and the composition of this application. For the reference electrode composition, the composition comprises styrene-butadiene rubber (SBR) and carboxymethyl cellulose (CMC). A urea-functionalized silicone material (also referred to herein as UPY) is added to the SBR / CMC mixture used for the test formulation. In all cases, the slurry is developed by adding the desired volume of water. The active materials used in the slurry comprise graphite, silica, and carbon black in a ratio of 80:14:1. The remaining 5% by weight of the composite comprises the composition of this application, which comprises a polymer, a urea-functionalized silicone material, and an electrode activator. A reference electrode composition comprising SBR and CMC in a 3:2 ratio was determined to be a suitable proportion to provide a well-integrated coating on the current collector surface. In the case of the test sample, the urea-functionalized silicone material is used with SBR and CMC in a ratio of SBR / CMC / urea-functionalized material = 2:1:1 to achieve a coating on the current collector. In a 100 gm test sample, 1 gm of UPY (1 wt%), 2 gm of SBR (2 wt%), and 1 gm of CMC (1 wt%) were used, based on the total weight of the electrode composition.

[0276] Electrode slurry development was carried out in a high-speed mixer, where, in the first step, appropriate amounts of electrode active material, graphite, and carbon black were mixed with silica at 2000 rpm for one minute. This mixing was repeated three times to achieve a homogeneous mixture. Subsequently, a calculated amount of SBR was added and the mixture was again mixed at 2000 rpm, repeated three times, at which point viscosity was observed in the composite. Following this, the CMC and a calculated amount of additives were added, and the mixture was mixed at 2000 rpm in the high-speed mixer, repeated three times. Finally, the required amount of water was added to achieve a thick slurry that could be coated onto the electrode. Homogeneous mixing of the water was also ensured by repeating the high-speed mixing at 2000 rpm three times.

[0277] The slurry was then coated onto the surface of a 50 µm thick current collector using a wire bar coater. The coated foil was then dried in a vacuum oven at 110°C for 6 hours, and coins were then cut from the foil for use in assembling 2032-coin batteries.

[0278] For the dry coating technique, the required amount of negative electrode active material (containing graphite, silicon monoxide, and carbon black) is first mixed with a binder containing nitrogen-containing silane additives. The composition is mixed at 120°C for 4 hours. Subsequently, the mixture is passed through a current collector foil via a double roller at high temperature, resulting in the formation of a coating on the current collector. After the coating is formed, a coin is cut from the foil and assembled into a coin cell as further described below.

[0279] The lithium-ion battery was manufactured in 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 on a Biologic BCS 805 to determine its electrochemical properties.

[0280] Electrochemical analysis of the urea-functionalized organosilicon (UPY) material of the SBR / CMC formulation was performed in a 2032 lithium-ion coin cell. The working electrode comprised graphite / SiO / CB, with carbon black (CB) added as a conductivity-enhancing component. As previously described, the coin cell was assembled in an argon-filled glove box, and a clean lithium coin was used as the counter electrode. Cyclic voltammograms (CVs) were initially recorded between 3.0 and 0.1 V, and ten charge / discharge cycles were recorded. The first discharge curve showed a trough between 1.4 and 1.1 V, indicating the formation of the SEI layer. A deep drop below 0.6 V was also noted, which is attributed to lithium-ion intercalation at interstitial sites in the graphite and along the edges. Figure 1 Cyclic voltammetry of a graphite / SiO / CB electrode with urea-functionalized organosilicon material (UPY) of the following formula is shown:

[0281]

[0282] The corresponding charge cycle shows a peak at ~0.5 V, attributed to the expulsion of lithium ions from the graphite / SiO matrix. Subsequent charge / discharge cycles exhibit high reproducibility, indicating the electrode's high stability and mechanical integrity. The high stability of the electrode with the high-expansion material can be attributed to the highly efficient binder formulation that helps maintain the electrode's mechanical integrity. No troughs were observed during the second and subsequent discharge cycles, indicating that SEI formation was limited to the first discharge cycle.

[0283] In addition, CV was performed on the reference cell, and the following observations were made. Although the fingerprint region of the peak appears in a similar voltage region, indicating similar electrochemical activity, the CV curve of the reference binder indicates a lower current density. Furthermore, instability during charge cycling was observed, indicating the poorer performance of the reference binder. The effect of the additive's presence is related to the long-term cycling stability and capacity retention of the electrode. Figure 2 The cyclic voltammogram of a cell with a graphite / SiO / CB electrode, wherein the graphite / SiO / CB electrode has no additives and has an SBR / CMC binder, is shown.

[0284] Cyclic stability was determined by 500 cycles at a current rate of 50 mA / g, and the calculated specific capacity is mentioned in Table 2.

[0285] Table 1. Specific capacity retention after 5000 cycles.

[0286]

[0287] The capacity was calculated for different cycles and tabulated as shown in Table 1. Note that at the end of 500 cycles, the capacity of the electrode composition of the present invention (column 2) was not retained at 77% (column 3, row 6) relative to the initial capacity. In contrast, the baseline composition (column 4 of Table 1) showed only 10% capacity retention after 500 cycles compared to its initial capacity. Figure 3 Displays charge / discharge curves for various number of cycles.

[0288] The foregoing description includes examples from this specification. Of course, for the purposes of describing this specification, it is impossible to describe all conceivable combinations of components or methods, but those skilled in the art will recognize that many further other combinations and arrangements are possible. Therefore, this specification is intended to cover all such substitutions, modifications, and variations, provided they fall within the spirit and scope of the appended claims. Furthermore, with respect to the use of the term "comprising" in the detailed description or claims, such a term is intended to be inclusive, and is used in a manner similar to the term "including," since "including" is interpreted as inclusive when used as a transitional word in a claim.

[0289] The foregoing description identifies various non-limiting embodiments of adhesive materials for electrochemical devices and their applications. Modifications can be made by those skilled in the art, as well as those who can manufacture and use the invention. The disclosed embodiments are for illustrative purposes only and are not intended to limit the scope of the invention or the subject matter set forth in the claims.

Claims

1. A composition comprising: (a) Polymer resin; (b) Compounds represented by formula (I) (I) Where R 1 '、R 2 '、R 3 '、R 4 '、R 5 'and R 6 'Independently selected from R 4 OR 5 and urea functional groups, wherein R 4 Independently selected from monovalent groups, said monovalent group being selected from straight-chain alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, cycloalkyl 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, which are selected from straight-chain alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, cycloalkyl 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' or b' is 0 - 500, provided that at least one of these a' or b' > 0; and at least one R 1 ', R 2 ', R 3 ', R 4 ', R 5 ', and / or R 6 ' is a ureido functional group; The urea functional group therein is represented by the following formula: Where R 1 and R 2 Each is independently selected from hydrogen and monovalent organic groups having 1 to 20 carbon atoms; R 3 It is a divalent straight-chain alkylene group having 1 to 20 carbon atoms, or a divalent branched alkylene group having 3 to 20 carbon atoms, each of which optionally contains one or more heteroatoms within the chain; X is selected from substituted or unsubstituted aromatic groups having 6 to 20 carbon atoms and heterocyclic groups containing 1 to 20 heteroatoms, wherein the aromatic groups and / or the heterocyclic groups are optionally substituted with alkyl groups having 1 to 12 carbon atoms, and optionally contain heteroatoms selected from O, N and / or S, and a ureidofunctional group; and wherein Z is oxygen; (c) Electrode activators; and (d) Optional adhesive.

2. The composition according to claim 1, wherein the polymer resin is selected from one or more of the following: polyethylene, polypropylene, polyethylene terephthalate, polymethyl methacrylate, aromatic polyamide, chitosan, alginate, polyacrylic acid, polyimide, cellulose, carboxymethyl cellulose, nitrocellulose; styrene-butadiene rubber (SBR), isoprene rubber, butadiene rubber, fluorinated elastomers, acrylonitrile-butadiene rubber (NBR), ethylene-propylene rubber; styrene-butadiene-styrene block copolymers and their hydrogenated products; EPDM (ethylene-propylene-diene terpolymer), styrene-ethylene-butadiene-styrene copolymer, styrene-isoprene-styrene block copolymers and their hydrogenated products; syndiotactic 1,2-polybutadiene, polyvinyl acetate, ethylene-vinyl acetate copolymers and propylene-α-olefin copolymers; polyvinylidene fluoride, polytetrafluoroethylene, vinylidene fluoride copolymers and tetrafluoroethylene-ethylene copolymers; and polymers containing alkali metal ions.

3. The composition according to claim 1 or 2, wherein the optional binder is selected from one or more of the following: carboxymethyl cellulose, methyl cellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, oxidized starch, monostarch phosphate, casein, polyvinylpyrrolidone, and its salts.

4. The composition according to any one of claims 1 to 3, wherein the electrode activator is selected from one or more of an intercalating agent and a conductive agent.

5. The composition according to claim 4, wherein the intercalator 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 w (0 < w ≦ 2).

6. The composition according to claim 4 or 5, wherein the conductive agent is a carbonaceous conductive agent selected from graphite, including natural graphite and artificial graphite; carbon black, including acetylene black, Ketjen black, channel black, furnace black, lamp black, and thermal cracking black; amorphous carbon, including needle coke; carbon nanotubes; fullerenes; and vapor-grown carbon fibers (VGCF).

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

8. The composition according to claim 7, wherein the compound of formula (I) has the following formula:

1. Where R 1' R 3' R 5' and R 6' Each independently selected from R 4 OR 5 and urea functional groups, wherein R 4 The group is independently selected from monovalent groups, which are selected from straight-chain alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, cycloalkyl 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, which are selected from straight-chain alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, cycloalkyl 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 1-500; and R 1' R 3' R 5' and R 6' At least one of them is selected from the urea functional group.

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

10. The composition according to any one of claims 1 to 9, wherein the compound represented by formula 1 is a urea-functionalized organosilicon.

11. The composition according to any one of claims 1 to 10, wherein the urea-functionalized organosilicon is a compound of the following formula: in, R 1 and R 2 Each is independently hydrogen or a monovalent organic group having 1 to 20 carbon atoms; R 3 It is a divalent straight-chain alkylene having 1 to 20 carbon atoms, or a divalent branched alkylene having 3 to 20 carbon atoms, each of which optionally contains one or more heteroatoms within the chain; R 4 Independently, it is a monovalent group selected from the following: straight-chain alkyl having 1 to 12 carbon atoms, branched alkyl having 3 to 12 carbon atoms, cycloalkyl having 5 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, aryl having 6 to 20 carbon atoms, and aralkyl having 7 to 20 carbon atoms; R 5 It is independently selected from straight-chain alkyl having 1 to 12 carbon atoms, branched alkyl having 3 to 12 carbon atoms, cycloalkyl having 5 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, aryl having 6 to 20 carbon atoms, and aralkyl 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, wherein the aromatic group or the heterocyclic group is optionally substituted with an alkyl group having 1 to 12 carbon atoms, and optionally contains a heteroatom selected from O, N and / or S, and a urea functional group: Z is oxygen; and a is an integer with the value 1, 2, or 3.

12. The composition according to any one of claims 1 to 6 or 9, wherein 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 in: M 1 For (R) 16 (R) 17 (R) 18 SiO 1 / 2 M 2 For (R) 19 (R) 20 (R) 21 SiO 1 / 2 D 1 For (R) 22 (R) 23 SiO 2 / 2 D 2 For (R) 24 (R) 25 SiO 2 / 2 T 1 For (R) 26 SiO 3 / 2 T 2 For (R) 27 SiO 3 / 2 Q is SiO 4 / 2 R 16 R 17 R 18 R 22 R 23 and R 26 Independently selected from R 4 and OR 5 ; R 19 R 20 R 21 R 24 R 25 and R 27 Independently selected from R 4 OR 5 and urea functional group, condition is R 19 R 20 R 21 R 24 R 25 and R 27 At least one of them is a urea functional group; Where R 4 The group is independently selected from monovalent groups, which are selected from straight-chain alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, cycloalkyl 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 It is independently selected from straight-chain alkyl having 1 to 12 carbon atoms, branched alkyl having 3 to 12 carbon atoms, cycloalkyl having 5 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, aryl having 6 to 20 carbon atoms, and aralkyl having 7 to 20 carbon atoms; b, d, and f are independent integers greater than 0; and a, c, e, and g are each an independent integer greater than 0.

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

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

15. The composition according to any one of claims 1 to 12, wherein X is selected from... ; ; ;and Where R 11 Selected from hydrogen and monovalent organic groups having 1 to 12 carbon atoms.

16. The composition according to any one of claims 1 to 12, wherein X is J1, J2, and J3 are each independently a substituted or unsubstituted C or N atom, and the dashed line between J1, J2, and J3 represents an optional double bond between J1 and J2 or between J2 and J3.

17. The composition according to any one of claims 1 to 12, wherein the substituent in X is represented by the following formula: Where R 6 and R 7 Each is independently hydrogen or a monovalent organic group having 1 to 20 carbon atoms; R 8 It is a divalent straight-chain alkylene having 1 to 20 carbon atoms, or a divalent branched alkylene having 3 to 20 carbon atoms, each of which may optionally contain one or more heteroatoms within the chain; R 9 Each is independently selected from a monovalent group, wherein the monovalent group is selected from a straight-chain alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a cycloalkyl 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 10 The group is independently selected from monovalent groups, wherein the monovalent group is selected from straight-chain alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, cycloalkyl 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 wherein b is an integer with the value 1, 2, or 3.

18. The composition according to claim 17, wherein the urea-functionalized organosilicon is represented by the following formula: 。 19. The composition according to any one of claims 1 to 18, wherein the compound represented by formula 1 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 1 is present in the following amounts: from about 0.01 wt% to about 90 wt%, from about 0.05 wt% to about 80 wt%, from about 0.1 wt% to about 75 wt%, from about 0.2 wt% to about 60 wt%, from about 0.5 wt% to about 50 wt%, from about 1 wt% to about 25 wt%, or from about 5 wt% to about 10 wt% based on the total weight of the composition; preferably 1-10 wt%, 10-50 wt%, or 50-90 wt% based on the total weight of the composition.

21. The composition according to any one of claims 1 to 19, wherein the composition is a solvent-free composition.

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

23. The energy storage device of claim 22, wherein the device has a specific capacity of at least 20% of its specific capacity after at least 500 electrochemical cycles, as determined by a cycle stability study.

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

25. The energy storage device according to any one of claims 22 to 24, wherein the device has a specific capacity of at least 60% of its specific capacity after the first cycle following at least 500 electrochemical cycles, as determined by a cycle stability study.

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

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

28. An energy storage device, comprising: at least one electrode and an electrolyte, wherein the at least one electrode comprises: (a) a polymeric resin; (b) a capacity-retaining agent; (c) an electrode activator; and (d) an optional binder, wherein the capacity-retaining agent maintains the specific capacity of the electrode in the range of 20-80% of its specific capacity after the first cycle after 500 electrochemical cycles.

29. The energy storage device according to claim 28, wherein the capacity-retaining agent is represented by the following formula: Where R 1 '、R 2 '、R 3 '、R 4 '、R 5 'and R 6 'Each is independent of R 4 OR 5 or urea functional group, wherein R 4 Independently, it is a straight-chain alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a cycloalkyl group having 5 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, and an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. R 5 Independently, it is a straight-chain alkyl group having 1 to 12 carbon atoms, a branched alkyl group having 3 to 12 carbon atoms, a cycloalkyl 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, or an aralkyl group having 7 to 20 carbon atoms. a' or b' is an integer having a value in the range of 0-500, provided that at least one of a' or b' is greater than 0; and R 1 '、R 2 '、R 3 '、R 4 '、R 5 'and / or R 6 At least one of the components is a urea functional group.

30. The energy storage device according to claim 29, wherein the urea functional group is represented by the following formula: Where R 1 and R 2 Each is independently selected from hydrogen and monovalent organic groups having 1 to 20 carbon atoms; R 3 It is a divalent straight-chain alkylene having 1 to 20 carbon atoms, or a divalent branched alkylene having 3 to 20 carbon atoms, each of which optionally contains one or more heteroatoms within the chain; X is selected from substituted or unsubstituted aromatic groups having 6 to 20 carbon atoms and heterocyclic groups containing 1 to 20 heteroatoms, wherein the aromatic groups and / or the heterocyclic groups are optionally substituted with alkyl groups having 1 to 12 carbon atoms, and optionally contain heteroatoms selected from O, N and / or S, and a urea functional group; and Z stands for oxygen.

31. An electrode comprising the composition according to any one of claims 1-21.

32. An electrochemical cell comprising a negative electrode and a positive electrode, wherein the negative electrode, the positive electrode, or both the negative electrode and the positive electrode comprise the composition according to claims 1-21.

33. The electrochemical cell according to claim 32, further comprising a separator.

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

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