JP2014522078A - Battery electrolyte materials and methods of use - Google Patents

Abstract

  Described herein are several desirable characteristics when incorporated into a battery, such as high stability during battery cycling to high temperatures and high voltages, high discharge capacity, high coulomb efficiency, And a material for use in an electrolyte that achieves excellent maintenance of discharge capacity and coulomb efficiency over several cycles of charge and discharge. In some embodiments, the high voltage electrolyte includes a base electrolyte and a set of additive compounds that provide these desirable performance characteristics.

Description

[001] This application claims the priority and benefit of each of the following applications. US Patent Provisional Application No. 61 / 495,318, filed June 9, 2011 entitled “Battery Electrics for High Voltage Cathode Materials”; “Battery Electrics for High Voltage Vol. 11” US Provisional Patent Application No. 61 / 543,262, filed Oct. 4, United States Patent Provisional Application No. 61 /, filed February 10, 2012 entitled “Battery Electrolytes for High Voltage Cathode Materials” 597,509; and “Materials for Battery Electrics and Methods” US patent application Ser. No. 13 / 459,702, filed Apr. 30, 2012, entitled “ds for Use”, each of which is incorporated herein by reference.

[002] The present invention relates generally to battery electrolytes. More specifically, the present invention relates to battery electrolytes for improving one or more of battery stability, eg, high voltage stability, thermal stability, electrochemical stability, and chemical stability. About.

[003] The electrolyte functions to transport ions and prevent electrical contact between the electrodes in the battery. Organic carbonate-based electrolytes are most commonly used in lithium-ion (“Li-ion”) batteries, and more recently efforts have been made to develop new classes of electrolytes based on sulfones, silanes, and nitriles. I came. Unfortunately, these conventional electrolytes are generally not stable at high voltages because they are unstable at over 4.5V or other high voltages. Conventional electrolytes at high voltages can be decomposed by, for example, catalytic oxidation in the presence of the positive electrode material to produce undesirable products that affect both battery performance and safety.

[004] Li- For ion batteries, cobalt and nickel-containing phosphate, fluorophosphate, fluoro sulfates, spinel, and _{silicate, LiFePO 4, LiMn 2 O 4} , and higher energy than the cathode material used for other general It has been reported to have a density. However, these positive electrode materials also have a redox potential of greater than 4.5V and can operate the battery at higher voltages, but can also lead to severe electrolyte decomposition in the battery. To use the cathode material to achieve higher energy density on higher voltage platforms, at least up to the oxidation-reduction potential of the cathode material or beyond the oxidation-reduction potential of the cathode material Should be tackled.

[005] Another problem for both organic carbonate electrolytes and other classes of electrolytes is chemical stability at high temperatures. Even at low voltages, high temperatures cause conventional electrolytes to decompose, for example, by catalytic oxidation in the presence of positive electrode materials, producing undesirable products that affect both battery performance and safety. Can be a factor.

[006] Against this background, there has been a need to develop the electrolytes and related methods and systems described herein. Certain embodiments of the invention disclosed herein address these and other challenges.

[007] Certain embodiments of the present invention are directed to electrolytes and electrolytes for high voltage batteries. The electrolytic solution contains a lithium salt, a non-aqueous solvent, and a compound represented by the formula (I).

（式中、Ｒ₁、Ｒ₂、およびＲ₃は、それぞれ独立に、置換および無置換Ｃ₁〜Ｃ₂₀アルキル基、置換および無置換Ｃ₁〜Ｃ₂₀アルケニル基、置換および無置換Ｃ₁〜Ｃ₂₀アルキニル基、ならびに置換および無置換Ｃ₅〜Ｃ₂₀アリール基からなる群より選択され、
Ｘは、窒素または酸素であり、
Ｙは、水素化物基、ハロ基、ヒドロキシ基、チオ基、アルキル基、アルケニル基、アルキニル基、アリール基、イミニル基、アルコキシ基、アルケノキシ基、アルキノキシ基、アリールオキシ基、カルボキシ基、アルキルカルボニルオキシ基、アルケニルカルボニルオキシ基、アルキニルカルボニルオキシ基、アリールカルボニルオキシ基、アルキルチオ基、アルケニルチオ基、アルキニルチオ基、アリールチオ基、シアノ基、Ｎ−置換アミノ基、アルキルカルボニルアミノ基、Ｎ−置換アルキルカルボニルアミノ基、アルケニルカルボニルアミノ基、Ｎ−置換アルケニルカルボニルアミノ基、アルキニルカルボニルアミノ基、Ｎ−置換アルキニルカルボニルアミノ基、アリールカルボニルアミノ基、およびＮ−置換アリールカルボニルアミノ基、ホウ素含有基、アルミニウム含有基、ケイ素含有基、リン含有基、および硫黄含有基からなる群より選択される。）
ある実施形態において、電解液は、約４．２Ｖ超の電圧での高電圧電池における電気化学的安定性を特徴とする。ある実施形態において、電解液は、電池が高温での環境中で作動するときの電気化学的安定性を特徴とする。

Wherein R ₁ , R ₂ , and R ₃ are each independently a substituted and unsubstituted C ₁ -C ₂₀ alkyl group, a substituted and unsubstituted C ₁ -C ₂₀ alkenyl group, a substituted and unsubstituted C _1- C ₂₀ alkynyl group, and is selected from the group consisting of substituted and unsubstituted C ₅ -C ₂₀ aryl group,
X is nitrogen or oxygen;
Y is a hydride group, halo group, hydroxy group, thio group, alkyl group, alkenyl group, alkynyl group, aryl group, iminyl group, alkoxy group, alkenoxy group, alkynoxy group, aryloxy group, carboxy group, alkylcarbonyloxy Group, alkenylcarbonyloxy group, alkynylcarbonyloxy group, arylcarbonyloxy group, alkylthio group, alkenylthio group, alkynylthio group, arylthio group, cyano group, N-substituted amino group, alkylcarbonylamino group, N-substituted alkylcarbonyl group Amino group, alkenylcarbonylamino group, N-substituted alkenylcarbonylamino group, alkynylcarbonylamino group, N-substituted alkynylcarbonylamino group, arylcarbonylamino group, and N-substituted arylcarbonylamino group Group, a boron-containing group, an aluminum-containing group, a silicon-containing group is selected from the group consisting of phosphorus-containing groups, and sulfur-containing groups. )
In certain embodiments, the electrolyte is characterized by electrochemical stability in high voltage batteries at voltages greater than about 4.2V. In certain embodiments, the electrolyte is characterized by electrochemical stability when the battery operates in an environment at high temperatures.

[008] Certain embodiments of the invention include a negative electrode having a negative electrode active material characterized by a first specific capacity, a positive electrode having a positive electrode active material characterized by a second specific capacity, a lithium salt, A battery including an aqueous solvent and an electrolytic solution containing a compound represented by the above formula (I) is an object. The first specific capacity and the second specific capacity are matched as indicated by the rated charge voltage of greater than about 4.2V. In certain embodiments, the battery is characterized by a specific capacity of at least about 10 mAh / (g of active material) when discharged at a current of about 0.01 C over a voltage range of about 4.9 V to about 4.2 V. Contains a positive electrode active material. In certain embodiments, when the battery operates in an environment at a temperature of about 50 degrees Celsius, the battery has a Coulomb efficiency of at least about 90% from the first cycle to 100 cycles.

[009] Other embodiments of the present invention are directed to methods of forming, conditioning, and operating a battery that includes such a high voltage and high temperature electrolyte. For example, a method of operating or using a battery can include preparing a battery and cycling such a battery, home appliances, portable appliances, hybrid vehicles, electric vehicles, power tools, power grids, military And powering for aerospace applications. For example, a method of forming a battery can include preparing a negative electrode, preparing a positive electrode, and preparing an electrolyte to promote current flow between the negative electrode and the positive electrode. . The electrolyte can include the electrolyte of certain embodiments of the present invention. The method of forming the battery can also include converting the stabilizing additive compound of the electrolyte to its derivative.

[010] Other aspects and embodiments of the invention are also contemplated. The above summary and the following detailed description are not meant to limit the invention to any particular embodiment, but are merely meant to describe some embodiments of the invention.

[011] Figure 2 illustrates a Li-ion battery incorporated according to one embodiment of the present invention. [012] FIG. 6 shows a diagram of the operation of a Li-ion battery and a non-limiting exemplary operation of an electrolyte solution containing an additive compound, according to one embodiment of the present invention. [013] Comparison of capacity retention with and without stabilizer over several cycles according to one embodiment of the present invention. 2 compares the coulombic efficiency with and without a stabilizer over several cycles according to one embodiment of the present invention. [014] Comparison of capacity retention with and without stabilizer over several cycles at 25 ° C. according to one embodiment of the present invention. [015] The results of the measurement of capacity retention at 50 ° C according to one embodiment of the present invention are superimposed on FIG. [016] Fig. 16 is a plot of capacity retention at 50 cycles versus stabilizer concentration, according to one embodiment of the invention. [017] FIG. 10 is a plot of Coulomb efficiency at cycle 50 versus stabilizer concentration, according to one embodiment of the invention. [018] Fig. 18 shows superimposed cyclic voltammograms for the first to third cycles according to one embodiment of the present invention. [019] Figure 8 shows superimposed cyclic voltammograms for cycles 4-6 according to one embodiment of the present invention. [020] Comparison of capacity retention with and without stabilizer over several cycles after aging according to one embodiment of the present invention. [021] Capacity with and without stabilizer over several cycles at 50 ° C. when using LiMn _1.5 Ni _0.5 O ₄ cathode material according to one embodiment of the present invention This is a comparison of maintenance rates. [022] Capacity retention with and without stabilizer over several cycles at 50 ° C. when using LiMn ₂ O ₄ cathode material according to one embodiment of the present invention Is a comparison. [023] Figure 7 illustrates an open circuit voltage measurement at 50 0 C according to one embodiment of the present invention. [024] Figure 8 illustrates a residual current measurement at a constant voltage at 50 0 C, according to one embodiment of the present invention. [025] Comparison of capacity retention with and without stabilizer over several cycles according to one embodiment of the present invention. [026] Comparison of capacity retention rates with a silicon-containing stabilizer and a silicon-free stabilizer according to one embodiment of the present invention. [027] A comparison of specific capacities during discharge at the 50th cycle for battery cells comprising various silicon-containing stabilizers according to one embodiment of the present invention. [028] Comparison of capacity retention of silicon-containing stabilizers over several cycles, according to one embodiment of the present invention. [029] A comparison of specific capacities during discharge in the 100th cycle with and without the use of a silicon-containing stabilizer in a conventional electrolyte according to an embodiment of the present invention. [030] This compares the specific capacities during discharge at different temperatures with and without the use of a silicon-containing stabilizer, according to one embodiment of the present invention. [031] A comparison of capacity retention rates at the 25th cycle with and without a silicon-containing stabilizer when using various positive electrode materials according to one embodiment of the present invention. [032] Figure 9 shows residual current measurements for battery cells held at about 4.5V, about 4.9V, and about 5.1V at 50 ° C for about 10 hours, according to one embodiment of the present invention. [033] Comparison of Coulombic efficiency with and without stabilizer over several cycles for a LiMn _1.5 Ni _0.5 O ₄ cathode material according to one embodiment of the present invention. [034] For doped LiCoPO ₄ cathode material according to one embodiment of the present invention, with and without stabilizer over several cycles after 8 days storage at 50 ° C The specific capacity at the time of discharge is compared. [035] Comparison of capacity retention rates with and without stabilizers at different charge and discharge rates according to one embodiment of the present invention. [036] Comparison of capacity retention rates with and without room temperature stabilizers when using LiMn _1.5 Ni _0.5 O ₄ cathode material according to one embodiment of the present invention. . [037] Figure 9 shows the voltage profile at the 1st and 100th cycles between charges with and without a stabilizer, according to one embodiment of the present invention. [038] Describes the voltage profile at the third cycle during discharge, with and without a stabilizer, according to one embodiment of the present invention. [039] This compares the Coulomb efficiency of battery cells with and without the use of a stabilizer in the first cycle. [040] Batteries with and without stabilizers over several cycles expressed as a percentage of initial specific capacity during discharge maintained in a particular cycle, according to one embodiment of the invention This is a comparison of the capacity retention rates of the cells. [041] Batteries with and without stabilizers over several cycles expressed as a percentage of the initial specific capacity during discharge maintained in a particular cycle, according to one embodiment of the present invention This is a comparison of the capacity retention rates of the cells. [042] This compares the Coulomb efficiency of battery cells with and without the use of a stabilizer in the first cycle according to one embodiment of the present invention. [043] Batteries with and without stabilizers over several cycles expressed as a percentage of the initial specific capacity during discharge maintained in a particular cycle, according to one embodiment of the invention This is a comparison of the capacity retention rates of the cells. [044] This compares the coulombic efficiency of battery cells with and without the use of a stabilizer in the first cycle, according to one embodiment of the present invention. [045] This compares the coulombic efficiency of battery cells with and without the use of a stabilizer in the first cycle according to one embodiment of the present invention. [046] Batteries with and without stabilizers over several cycles expressed as a percentage of the initial specific capacity during discharge maintained in a particular cycle, according to one embodiment of the invention This is a comparison of the capacity retention rates of the cells. Battery cell capacity with and without stabilizer over several cycles expressed as a percentage of initial specific capacity during discharge maintained in a particular cycle, according to one embodiment of the present invention This is a comparison of maintenance rates. Battery cell capacity with and without stabilizer over several cycles expressed as a percentage of initial specific capacity during discharge maintained in a particular cycle, according to one embodiment of the present invention This is a comparison of maintenance rates. Battery cell capacity with and without stabilizer over several cycles expressed as a percentage of initial specific capacity during discharge maintained in a particular cycle, according to one embodiment of the present invention This is a comparison of maintenance rates. Battery cell capacity with and without stabilizer over several cycles expressed as a percentage of initial specific capacity during discharge maintained in a particular cycle, according to one embodiment of the present invention This is a comparison of maintenance rates. Battery cell capacity with and without stabilizer over several cycles expressed as a percentage of initial specific capacity during discharge maintained in a particular cycle, according to one embodiment of the present invention This is a comparison of maintenance rates. Battery cell capacity with and without stabilizer over several cycles expressed as a percentage of initial specific capacity during discharge maintained in a particular cycle, according to one embodiment of the present invention This is a comparison of maintenance rates. Battery cell capacity with and without stabilizer over several cycles expressed as a percentage of initial specific capacity during discharge maintained in a particular cycle, according to one embodiment of the present invention This is a comparison of maintenance rates. [047] Comparison of the energy efficiency of battery cells with and without stabilizers over several cycles, according to one embodiment of the present invention. [048] Batteries with and without stabilizers over several cycles expressed as a percentage of the initial specific capacity during discharge maintained in a particular cycle, according to one embodiment of the present invention This is a comparison of the capacity retention rates of the cells. Battery cell capacity with and without stabilizer over several cycles expressed as a percentage of initial specific capacity during discharge maintained in a particular cycle, according to one embodiment of the present invention This is a comparison of maintenance rates.

[049] The following definitions apply to some of the aspects described with respect to some embodiments of the invention. These definitions extend as well from the description herein. Each term is further explained and illustrated throughout the description, drawings, and examples. Any interpretation of terms in this description should take into account the entire description, drawings, and examples presented herein.

[050] As used herein, the singular terms "a", "an", and "the" may refer to the plural subject unless the context clearly dictates otherwise. Including. Thus, for example, reference to a subject can include a plurality of subjects unless the context clearly indicates otherwise.

[051] As used herein, the term "set" refers to a collection of one or more objects. Thus, for example, a set of subjects may include a single subject or multiple subjects. A set of objects can also be referred to as a member of the set. A set of objects may be the same or different. In some cases, a set of objects may share one or more common characteristics.

[052] As used herein, the terms "substantially" and "substantially" refer to a significant degree or degree. When used in conjunction with an event or situation, these terms refer to examples where the event or situation occurs exactly as well as examples where the event or situation occurs (typical of the embodiments described herein). An example of constructing an acceptable tolerance or variation).

[053] As used herein, the term "submicron range" refers to less than about 1 μm or less than about 1,000 nm, such as less than about 999 nm, less than about 900 nm, less than about 800 nm, less than about 700 nm, about 600 nm. Refers to a general range of dimensions of less than, less than about 500 nm, less than about 400 nm, less than about 300 nm, or less than about 200 nm, and up to or less than about 1 nm. In some cases, the term includes, for example, about 1 nm to about 100 nm, about 100 nm to about 200 nm, about 200 nm to about 300 nm, about 300 nm to about 400 nm, about 400 nm to about 500 nm, about 500 nm to about 600 nm, about 600 nm to about It can refer to a specific sub-range within the general range, such as 700 nm, about 700 nm to about 800 nm, about 800 nm to about 900 nm, or about 900 nm to about 999 nm.

[054] As used herein, the term "typical element" refers to Group IA (or Group 1), Group IIA (or Group 2), Group IIIA (or Group 13), Group IVA (or Group 14) , VA (or 15), VIA (or 16), VIIA (or 17), and VIIIA (or 18). The typical element may be referred to as an s block element or a p block element.

[055] As used herein, the term "transition metal" refers to Group IVB (or Group 4), Group VB (or Group 5), Group VIB (or Group 6), Group VIIB (or Group 7). , VIIIB (or Groups 8, 9, and 10), IB (or Group 11), and IIB (or Group 12). Transition metals are sometimes referred to as d-block elements.

[056] As used herein, the term "rare earth element" refers to Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb. , And Lu.

[057] As used herein, the term "halogen" refers to any of F, Cl, Br, I, and At.

[058] As used herein, the term "chalcogen" refers to any of O, S, Se, Te, and Po.

[059] As used herein, the term "heteroatom" refers to any atom that is not a carbon atom or a hydrogen atom. Hetero atoms include atoms of halogen, chalcogen, group IIIA (or group 13) elements, group IVA (or group 14) elements other than carbon, and group VA (or group 15) elements.

[060] As used herein, the term "alkane" refers to a saturated hydrocarbon comprising a more specific definition of "alkane" herein. For certain embodiments, the alkane can contain 1 to 100 carbon atoms. The term “lower alkane” refers to an alkane containing 1 to 20 carbon atoms, such as 1 to 10 carbon atoms, while the term “higher alkane” refers to more than 20 carbon atoms, for example, Refers to alkanes containing 21 to 100 carbon atoms. The term “branched alkane” refers to an alkane that contains one or more branches, while the term “unbranched alkane” refers to a linear alkane. The term “cycloalkane” refers to an alkane comprising one or more cyclic structures. The term “heteroalkane” refers to an alkane in which one or more of its carbon atoms is replaced by one or more heteroatoms, eg, N, Si, S, O, F, and P. The term “substituted alkane” refers to an alkane in which one or more of its hydrogen atoms is replaced by one or more substituents, eg, a halo group, while the term “unsubstituted alkane” is Refers to an alkane having no substituent. Combinations of the above terms can be used to refer to alkanes having a combination of properties. For example, the term “branched lower alkane” can be used to refer to an alkane containing 1 to 20 carbon atoms and one or more branches. Examples of alkanes include methane, ethane, propane, cyclopropane, butane, 2-methylpropane, cyclobutane, and their charged, hetero, or substituted forms.

[061] As used herein, the term "alkyl group" refers to a monovalent form of an alkane that includes the more specific definition of "alkyl" herein. For example, an alkyl group can be depicted as an alkane in which one of its hydrogen atoms has been removed and can be attached to another group. The term “lower alkyl group” refers to a monovalent form of a lower alkane, while the term “higher alkyl group” refers to a monovalent form of a higher alkane. The term “branched alkyl group” refers to a monovalent form of a branched alkane, while the term “unbranched alkyl group” refers to a monovalent form of an unbranched alkane. The term “cycloalkyl group” refers to a monovalent form of a cycloalkane, and the term “heteroalkyl group” refers to a monovalent form of a heteroalkane. The term “substituted alkyl group” refers to a monovalent form of a substituted alkane, while the term “unsubstituted alkyl group” refers to a monovalent form of an unsubstituted alkane. Examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, butyl, isobutyl, t-butyl, cyclobutyl, and their charged, hetero, or substituted forms.

[062] As used herein, the term "alkylene group" refers to a divalent form of an alkane that includes a more specific definition of an "alkylene group" herein. For example, an alkylene group can be depicted as an alkane in which two of its hydrogen atoms have been removed to allow attachment to one or more additional groups. The term “lower alkylene group” refers to the divalent form of the lower alkane, while the term “higher alkylene group” refers to the divalent form of the higher alkane. The term “branched alkylene group” refers to a divalent form of a branched alkane, while the term “unbranched alkylene group” refers to a divalent form of an unbranched alkane. The term “cycloalkylene group” refers to the divalent form of the cycloalkane, and the term “heteroalkylene group” refers to the divalent form of the heteroalkane. The term “substituted alkylene group” refers to the divalent form of a substituted alkane, while the term “unsubstituted alkylene group” refers to the divalent form of an unsubstituted alkane. Examples of alkylene groups include methylene, ethylene, propylene, 2-methylpropylene, and their charged, hetero, or substituted forms.

[063] As used herein, the term "alkene" refers to an unsaturated hydrocarbon containing one or more carbon-carbon double bonds that includes a more specific definition of "alkene" herein. Point to. For certain embodiments, the alkene can contain from 2 to 100 carbon atoms. The term “lower alkene” refers to an alkene containing 2 to 20 carbon atoms, eg 2 to 10 carbon atoms, whereas the term “higher alkene” is greater than 20 carbon atoms, eg Refers to alkenes containing 21 to 100 carbon atoms. The term “cycloalkene” refers to an alkene containing one or more cyclic structures. The term “heteroalkene” refers to an alkene in which one or more of its carbon atoms has been replaced by one or more heteroatoms, eg, N, Si, S, O, F, and P. The term “substituted alkene” refers to an alkene in which one or more of its hydrogen atoms is replaced by one or more substituents, eg, a halo group, while the term “unsubstituted alkene” is This refers to an alkene having no substituent. A combination of the above terms can be used to refer to an alkene having a combination of properties. For example, the term “substituted lower alkene” can be used to refer to an alkene containing 1 to 20 carbon atoms and one or more substituents. Examples of alkenes include ethene, propene, cyclopropene, 1-butene, trans-2 butene, cis-2-butene, 1,3-butadiene, 2-methylpropene, cyclobutene, and their charged, hetero, or substituted The form is mentioned.

[064] As used herein, the term "alkenyl group" refers to a monovalent form of an alkene containing a more specific definition of "alkenyl group" herein. For example, an alkenyl group can be depicted as an alkene in which one of its hydrogen atoms has been removed and allowed to bond to another group. The term “lower alkenyl group” refers to the monovalent form of the lower alkene, while the term “higher alkenyl group” refers to the monovalent form of the higher alkene. The term “cycloalkenyl group” refers to a monovalent form of a cycloalkene, and the term “heteroalkenyl group” refers to a monovalent form of a heteroalkene. The term “substituted alkenyl group” refers to a monovalent form of a substituted alkene, while the term “unsubstituted alkenyl group” refers to a monovalent form of an unsubstituted alkene. Examples of alkenyl groups include ethenyl, 2-propenyl (ie, allyl), isopropenyl, cyclopropenyl, butenyl, isobutenyl, t-butenyl, cyclobutenyl, and their charged, hetero, or substituted forms.

[065] As used herein, the term "alkenylene group" refers to a divalent form of an alkene that includes a more specific definition of "alkenylene group" herein. For example, an alkenylene group can be depicted as an alkene in which two of its hydrogen atoms have been removed to allow attachment to one or more additional groups. The term “lower alkenylene group” refers to the divalent form of the lower alkene, while the term “higher alkenylene group” refers to the divalent form of the higher alkene. The term “cycloalkenylene group” refers to the divalent form of the cycloalkene, and the term “heteroalkenylene group” refers to the divalent form of the heteroalkene. The term “substituted alkenylene group” refers to the divalent form of the substituted alkene, while the term “unsubstituted alkenylene group” refers to the divalent form of the unsubstituted alkene. Examples of alkenyl groups include ethenylene, propenylene, 2-methylpropenylene, and their charged, hetero, or substituted forms.

[066] As used herein, the term "alkyne" refers to an unsaturated hydrocarbon containing one or more carbon-carbon triple bonds that includes the more specific definition of "alkyne" herein. Point to. In some embodiments, the alkyne can also include one or more carbon-carbon double bonds. For certain embodiments, the alkyne can contain 2 to 100 carbon atoms. The term “lower alkyne” refers to an alkyne containing 2 to 20 carbon atoms, such as 2 to 10 carbon atoms, while the term “higher alkyne” refers to more than 20 carbon atoms, for example, Refers to alkynes containing 21 to 100 carbon atoms. The term “cycloalkyne” refers to an alkyne containing one or more cyclic structures. The term “heteroalkyne” refers to an alkyne in which one or more of its carbon atoms is replaced by one or more heteroatoms, eg, N, Si, S, O, F, and P. The term “substituted alkyne” refers to an alkyne in which one or more of its hydrogen atoms has been replaced by one or more substituents, eg, a halo group, while the term “unsubstituted alkyne” It refers to an alkyne having no substituent. A combination of the above terms can be used to refer to an alkyne having a combination of properties. For example, the term “substituted lower alkyne” can be used to refer to an alkyne containing 1 to 20 carbon atoms and one or more substituents. Examples of alkynes include ethyne (ie, acetylene), propyne, 1-butyne, 1-butene-3-yne, 1-pentyne, 2-pentyne, 3-pentene-1-yne, 1-pentene-4-yne , 3-methyl-1-butyne, and their charged, hetero, or substituted forms.

[067] As used herein, the term "alkynyl group" refers to a monovalent form of an alkyne that includes a more specific definition of "alkynyl group" herein. For example, an alkynyl group can be depicted as an alkyne in which one of its hydrogen atoms has been removed and allowed to bond to another group. The term “lower alkynyl group” refers to the monovalent form of the lower alkyne, while the term “higher alkynyl group” refers to the monovalent form of the higher alkyne. The term “cycloalkynyl group” refers to the monovalent form of cycloalkyne, and the term “heteroalkynyl group” refers to the monovalent form of heteroalkyne. The term “substituted alkynyl group” refers to a monovalent form of a substituted alkyne, while the term “unsubstituted alkynyl group” refers to a monovalent form of an unsubstituted alkyne. Examples of alkynyl groups include ethynyl, propynyl, isopropynyl, butynyl, isobutynyl, t-butynyl, and their charged, hetero, or substituted forms.

[068] As used herein, the term "alkynylene group" refers to a divalent form of an alkyne that includes a more specific definition of "alkynylene group" herein. For example, an alkynylene group can be depicted as an alkyne in which two of its hydrogen atoms have been removed to allow attachment to one or more additional groups on the molecule. The term “lower alkynylene group” refers to the divalent form of the lower alkyne, while the term “higher alkynylene group” refers to the divalent form of the higher alkyne. The term “cycloalkynylene group” refers to the divalent form of cycloalkyne, and the term “heteroalkynylene group” refers to the divalent form of heteroalkyne. The term “substituted alkynylene group” refers to the divalent form of a substituted alkyne, while the term “unsubstituted alkynylene group” refers to the divalent form of an unsubstituted alkyne. Examples of alkynylene groups include ethynylene, propynylene, 1-butynylene, 1-butene-3-inylene, and their charged, hetero, or substituted forms.

[069] As used herein, the term "arene" refers to an aromatic hydrocarbon comprising a more specific definition of "arene" herein. For certain embodiments, the arenes can contain from 5 to 100 carbon atoms. The term “lower arene” refers to an arene containing 5 to 20 carbon atoms, such as 5 to 14 carbon atoms, while the term “higher arene” is greater than 20 carbon atoms, for example, Refers to arenes containing 21 to 100 carbon atoms. The term “monocyclic arene” refers to an arene comprising a single aromatic cyclic structure, while the term “polycyclic arene” refers to a plurality of aromatic cyclic structures, eg, via a carbon-carbon bond. Arenes containing two or more aromatic cyclic structures that are linked together or fused together. The term “heteroarene” refers to an arene in which one or more of its carbon atoms has been replaced by one or more heteroatoms, eg, N, Si, S, O, F, and P. The term “substituted arene” means that one or more of its hydrogen atoms are one or more substituents such as alkyl, alkenyl, alkynyl, halo, hydroxy, alkoxy, alkenoxy, alkynoxy , Aryloxy group, carboxy group, cyano group, nitro group, amino group, N-substituted amino group, silyl group, and arene group replaced by siloxy group, while the term “unsubstituted arene” Refers to an arene having no substituent. A combination of the above terms can be used to refer to an arene having a combination of properties. For example, the term “monocyclic lower alkene” can be used to refer to an arene that contains 5 to 20 carbon atoms and a single aromatic ring structure. Examples of arenes include benzene, biphenyl, naphthalene, anthracene, pyridine, pyridazine, pyrimidine, pyrazine, quinoline, isoquinoline, and their charged, hetero, or substituted forms.

[070] As used herein, the term "aryl group" refers to a monovalent form of an arene that includes a more specific definition of "aryl group" herein. For example, an aryl group can be depicted as an arene in which one of its hydrogen atoms has been removed and allowed to bond to another group. The term “lower aryl group” refers to the monovalent form of the lower arene, while the term “higher aryl group” refers to the monovalent form of the higher arene. The term “monocyclic aryl group” refers to a monovalent form of a monocyclic arene, while the term “polycyclic aryl group” refers to a monovalent form of a polycyclic arene. The term “heteroaryl group” refers to a monovalent form of a heteroarene. The term “substituted aryl group” refers to a monovalent form of a substituted arene, while the term “unsubstituted arene group” refers to a monovalent form of an unsubstituted arene. Examples of aryl groups include phenyl, biphenylyl, naphthyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, quinolyl, isoquinolyl, and their charged, hetero, or substituted forms.

[071] As used herein, the term "imine" refers to an organic compound that contains one or more carbon-nitrogen double bonds, including the more specific definition of "imine" herein. . For certain embodiments, the imine can contain 1 to 100 carbon atoms. The term “lower imine” refers to an imine containing 1 to 20 carbon atoms, such as 1 to 10 carbon atoms, while the term “higher imine” refers to more than 20 carbon atoms, for example, Refers to an imine containing 21-100 carbon atoms. The term “cycloimine” refers to an imine containing one or more cyclic structures. The term “heteroimine” refers to an imine in which one or more of its carbon atoms is replaced by one or more heteroatoms, eg, N, Si, S, O, F, and P. The term “substituted imine” refers to an imine in which one or more of its hydrogen atoms is replaced by one or more substituents, eg, a halo group, while the term “unsubstituted imine” is Refers to an imine having no substituent. A combination of the above terms can be used to refer to an imine having a combination of properties. For example, the term “substituted lower imine” can be used to refer to an imine containing from 1 to 20 carbon atoms and one or more substituents. Examples of imines include R ₁ CH═NR ₂ , wherein R ₁ and R ₂ are each independently selected from a hydride group, an alkyl group, an alkenyl group, and an alkynyl group.

[072] As used herein, the term "iminyl group" refers to a monovalent form of an imine that includes the more specific definition of "iminyl" herein. For example, an iminyl group can be depicted as an imine in which one of its hydrogen atoms has been removed and allowed to bond to another group. The term “lower iminyl group” refers to the monovalent form of a lower imine, while the term “higher iminyl group” refers to the monovalent form of a higher imine. The term “cycloiminyl group” refers to the monovalent form of cycloimine, and the term “heteroiminyl group” refers to the monovalent form of heteroimine. The term “substituted imineyl group” refers to a monovalent form of a substituted imine, while the term “unsubstituted imineyl group” refers to a monovalent form of an unsubstituted imine. Examples of iminyl groups include —R ₁ CH═NR ₂ , R ₃ CH═NR ₄ —, —CH═NR ₅ , and R ₆ CH═N—, wherein R ₁ and R ₄ are each independently , An alkylene group, an alkenylene group, and an alkynylene group, and R ₂ , R ₃ , R ₅ , and R ₆ are each independently selected from a hydride group, an alkyl group, an alkenyl group, and an alkynyl group.

[073] As used herein, the term "alcohol" refers to an organic compound that contains one or more hydroxy groups. For certain embodiments, an alcohol can also be referred to as a substituted hydrocarbon, eg, a substituted arene, in which one or more of its hydrogen atoms are replaced by one or more hydroxy groups. Examples of alcohols include ROH, where R is selected from alkyl groups, alkenyl groups, alkynyl groups, and aryl groups.

[074] As used herein, the term "ketone" refers to a molecule comprising one or more groups of the form: -CO-. Examples of ketones include R ₁ —CO—R ₂ , wherein R ₁ and R ₂ are each independently an alkyl group, alkenyl group, alkynyl group, and aryl group, and R ₃ —CO—R ₄ —. Selected from CO—R ₅ , R ₃ and R ₅ are each independently selected from alkyl groups, alkenyl groups, alkynyl groups, and aryl groups, and R ₄ is selected from alkylene groups, alkenylene groups, and alkynylene groups Is done.

[075] As used herein, the term "carboxylic acid" refers to an organic compound that contains one or more carboxy groups. For certain embodiments, a carboxylic acid can also be referred to as a substituted hydrocarbon, for example, a substituted arene, in which one or more of its hydrogen atoms are replaced by one or more carboxy groups. Examples of carboxylic acids include RCOOH, where R is selected from alkyl groups, alkenyl groups, alkynyl groups, and aryl groups.

[076] As used herein, the term "hydride group" refers to -H.

[077] As used herein, the term "halo group" refers to -X, where X is a halogen. Examples of halo groups include fluoro, chloro, bromo, and iodo.

[078] As used herein, the term "hydroxy group" refers to -OH.

[079] As used herein, the term "alkoxy group" refers to -OR, and R is an alkyl group.

[080] As used herein, the term "alkenoxy group" refers to -OR and R is an alkenyl group.

[081] As used herein, the term "alkynoxy group" refers to -OR and R is an alkynyl group.

[082] As used herein, the term "aryloxy group" refers to -OR, where R is an aryl group.

[083] As used herein, the term "carboxy group" refers to -COOH.

[084] As used herein, the term "alkylcarbonyloxy group" refers to RCOO-, where R is an alkyl group.

[085] As used herein, the term "alkenylcarbonyloxy group" refers to RCOO-, where R is an alkenyl group.

[086] As used herein, the term "alkynylcarbonyloxy group" refers to RCOO-, where R is an alkynyl group.

[087] As used herein, the term "arylcarbonyloxy group" refers to RCOO-, where R is an aryl group.

[088] As used herein, the term "thio group" refers to -SH.

[089] As used herein, the term "alkylthio group" refers to -SR, where R is an alkyl group.

[090] As used herein, the term "alkenylthio group" refers to -SR, where R is an alkenyl group.

[091] As used herein, the term "alkynylthio group" refers to -SR, where R is an alkynyl group.

[092] As used herein, the term "arylthio group" refers to -SR, where R is an aryl group.

[093] As used herein, the term "cyano group" refers to -CN.

[094] As used herein, the term "nitro" refers to -NO _2.

[095] As used herein, the term "amino group" refers to -NH _2.

[096] As used herein, the term "N-substituted amino group" refers to an amino group in which one or more of its hydrogen atoms has been replaced by one or more substituents. Examples of N-substituted amino groups include —NR ₁ R ₂ , wherein R ₁ and R ₂ are each independently selected from a hydride group, an alkyl group, an alkenyl group, an alkynyl group, and an aryl group, At least one of R ₁ and R ₂ is not a hydride group.

[097] As used herein, the term "alkylcarbonylamino group" refers to -NHCOR, wherein R is an alkyl group.

[098] As used herein, the term "N-substituted alkylcarbonylamino group" refers to an alkylcarbonylamino group in which the hydrogen atom is replaced by a substituent. Examples of N-substituted alkylcarbonylamino groups include —NR ₁ COR ₂ , wherein R ₁ is selected from alkyl groups, alkenyl groups, alkynyl groups, and aryl groups, and R ₂ is an alkyl group.

[099] As used herein, the term "alkenylcarbonylamino group" refers to -NHCOR, wherein R is an alkenyl group.

[0100] As used herein, the term "N-substituted alkenylcarbonylamino group" refers to an alkenylcarbonylamino group whose hydrogen atom is replaced by a substituent. Examples of N-substituted alkenylcarbonylamino groups include —NR ₁ COR _2, where R ₁ is selected from alkyl groups, alkenyl groups, alkynyl groups, and aryl groups, and R ₂ is an alkenyl group.

[0101] As used herein, the term "alkynylcarbonylamino group" refers to -NHCOR, wherein R is an alkynyl group.

[0102] As used herein, the term "N-substituted alkynylcarbonylamino group" refers to an alkynylcarbonylamino group whose hydrogen atom is replaced by a substituent. Examples of N-substituted alkynylcarbonylamino groups include —NR ₁ COR ₂ , wherein R ₁ is selected from alkyl groups, alkenyl groups, alkynyl groups, and aryl groups, and R ₂ is an alkynyl group.

[0103] As used herein, the term "arylcarbonylamino group" refers to -NHCOR, wherein R is an aryl group.

[0104] As used herein, the term "N-substituted arylcarbonylamino group" refers to an arylcarbonylamino group whose hydrogen atom is replaced by a substituent. Examples of N-substituted arylcarbonylamino groups include —NR ₁ COR ₂ , wherein R ₁ is selected from alkyl groups, alkenyl groups, alkynyl groups, and aryl groups, and R ₂ is an aryl group.

[0105] As used herein, the term "silyl group" refers to -SiR ₁ R ₂ R ₃ , where R ₁ , R ₂ , and R ₃ are each independently, for example, a hydride group, It is selected from alkyl groups, alkenyl groups, alkynyl groups, and aryl groups.

[0106] As used herein, the term "siloxy group" refers to _{-OSiR 1 R 2 R 3, R} 1, R 2, and R _3, for example, each independently, hydride radical, It is selected from alkyl groups, alkenyl groups, alkynyl groups, and aryl groups.

[0107] As used herein, the term "ether linkage" refers to -O-.

[0108] As used herein, the term "specific capacity" refers to the amount (eg, total or maximum) of electrons or lithium ions that a material can hold (or discharge) per unit mass. , And can be expressed in units of mAh / g. In certain aspects and embodiments, the specific capacity may be measured in a constant current discharge (or charge) analysis that includes a discharge (or charge) at a specific rate over a specific voltage range for a specific counter electrode. it can. For example, specific capacity can be measured by discharge at a rate of about 0.05 C (eg, about 7.5 mA / g) at 4.95 V to 2.0 V relative to the Li / Li ⁺ counter electrode. Other discharge rates and other voltage ranges, eg, about 0.1 C (eg, about 15 mA / g), or about 0.5 C (eg, about 75 mA / g), or about 1.0 C (eg, about 150 mA / g) The rate of g) can also be used.

[0109] As used herein, the rate "C" is the "1C" current at which a battery (substantially) (substantially fully charged) discharges substantially fully in one hour. The discharge current as a fraction or a multiple of the value, or the charge current as a fraction or a multiple of the “1C” current value at which the battery (substantially fully discharged) is substantially fully charged in one hour. Point to either.

[0110] As used herein, the term "cycle" or "cycling" refers to complementary discharging and charging processes.

[0111] As used herein, the term "rated charge voltage" refers to the upper end of a voltage range during battery operation, eg, the maximum voltage during battery charge, discharge, and / or cycling. . In some aspects and in some embodiments, the nominal charge voltage is that (from a substantially fully discharged state in the initial cycle, eg, the first cycle, the second cycle, or the third cycle). Maximum) Refers to the maximum voltage for charging the battery through the specific capacity. In some aspects and in some embodiments, the rated charging voltage is one or more of its performance characteristics, such as one or more of coulomb efficiency, maintenance of specific capacity, maintenance of energy density, and rate performance. Refers to the maximum voltage during operation of the battery to maintain substantially.

[0112] As used herein, the term "rated cut-off voltage" refers to the lower end of the voltage range during battery operation, eg, the minimum voltage during battery charging, discharging, and / or cycling. Point to. In some aspects and in some embodiments, the nominal cutoff voltage is a value from a substantially fully charged state in an initial cycle, e.g., first cycle, second cycle, or third cycle. It refers to the minimum voltage during discharge of the battery through the (maximum) specific capacity, and in such aspects and embodiments, the rated cut-off voltage can also be referred to as the rated discharge voltage. In some aspects and in some embodiments, the rated cutoff voltage is one or more of its performance characteristics, eg, one or more of coulomb efficiency, specific capacity maintenance, energy density maintenance, and rate performance. Is the minimum voltage during operation of the battery to substantially maintain

[0113] As used herein, "maximum voltage" refers to the voltage at which both the negative and positive electrodes are fully charged. In an electrochemical cell, each electrode may have a given specific capacity, once one electrode is fully charged, the other electrode is as far as possible for that particular pairing of electrodes. The electrode is limited in capacity so that it is fully charged. The process of matching the specific capacity of the electrodes to achieve the desired capacity of the electrochemical cell is “capacity matching”.

[0114] To the extent that specific battery characteristics can vary with temperature, such characteristics are defined at room temperature (25 ° C) unless the context clearly indicates otherwise.

[0115] Certain embodiments of the present invention provide high stability during battery cycling to high voltages above 4.2V, high specific capacity during charge or discharge, high coulomb efficiency, some of charge and discharge. When incorporated into a battery, such as excellent maintenance of specific capacity and energy density over the cycle, high rate performance, reduced electrolyte decomposition, reduced resistance and increased resistance during cycling, and improved calendar life It relates to an electrolyte that achieves several desirable features. The electrolyte achieves these performance characteristics over a wide range of operating temperatures, including about −40 ° C. or lower and up to about 60 ° C., up to about 80 ° C., or beyond. In some embodiments, these performance characteristics may be derived at least in part from the presence of a set of additives or compounds, while those additives or compounds maintain or improve battery performance. Can give high voltage and high temperature stability to electrolyte,

[0116] For example, with respect to their stability, batteries incorporating an electrolyte solution are at least as measured against a redox potential of a high voltage positive electrode material, for example, against a lithium metal negative electrode (Li / Li ⁺ negative electrode). Some embodiments of the invention when cycled to about 4.2V or about 4.5V, and up to about 4.95V, up to about 5V, up to about 5.5V, up to about 6V, or beyond Electrolytes containing compounds according to can cause little or no degradation (in association with film formation at the battery electrode or past initial degradation as part of the initial cycling). These voltages may vary for other counter electrodes, but improved performance is maintained by some embodiments. Such a reduction in electrolyte decomposition results in one or more of the following advantages. (1) Reduction of electrolyte loss; (2) Reduction of undesirable by-products that may affect battery performance; (3) Generation of gaseous by-products that may affect battery safety. And (4) reducing resistance and increasing resistance during cycling.

[0117] Also, a battery incorporating an electrolyte containing a compound according to a specific embodiment has a high Coulomb efficiency, expressed as the ratio of the specific capacity during discharge and the specific capacity during charge for a given cycle. Can show. Incorporated improved electrolyte when measured at cycling at a rate of 1C (or another reference rate higher or lower than 1C, eg, 0.1C, 0.05C, 0.5C, 5C, or 10C) The battery is at least about 60%, such as at least about 70%, at least about 80%, at least about 90%, or at least about 95%, and up to about 97%, up to about 98%, up to about 99%, up to about 99%. Up to .8%, up to about 99.9%, up to about 99.99%, up to about 99.999%, or beyond, the first cycle (or another initial cycle, eg, the second cycle, Cycle, 4th cycle, 5th cycle, 6th cycle, 7th cycle, 8th cycle, 9th cycle, or 10th cycle) Or cycle initial set of, for example, cycles 1-3, cycle 1-5, cycle 3-10, may have an average coulombic efficiency over the cycle 5-10 or cycle 5-15. Stated otherwise, and another reference current of 150 mA / g (or higher or lower than 150 mA / g, for example, 15 mA / g, 7.5 mA / g, 75 mA / g, 750 mA / g, or 1, A battery incorporating an electrolyte comprising a compound of certain embodiments, as measured by cycling at a substantially constant current of 500 mA / g), is at least about 60%, such as at least about 70%, at least about 80%, At least about 90%, or at least about 95%, and up to about 97%, up to about 98%, up to about 99%, up to about 99.8%, up to about 99.9%, up to about 99.99%, about 1st cycle (or another initial cycle, for example, 2nd cycle, 3rd cycle, 4th cycle, 5th cycle, up to 99.999% or more Cycle, 7th cycle, 8th cycle, 9th cycle, or 10th cycle), or an initial set of cycles, for example, cycles 1 to 3, cycles 1 to 5, cycles 3 to 10, cycle 5 Can have an average Coulomb efficiency over 10 to 10 or cycles 5 to 15. The value described for the current may be per unit mass of the positive electrode active material and can be expressed in units of mA / (g of positive electrode active material).

[0118] In addition, batteries incorporating an electrolyte comprising a compound of certain embodiments can span several charge and discharge cycles, eg, from the first cycle to 100 cycles, 200 cycles, 300 cycles, 400 cycles. After 500 cycles, 600 cycles, 1,000 cycles, or even 5,000 cycles, it can show excellent capacity retention defined in terms of specific capacity (both during charging and discharging). By cycling at a rate (or another reference rate higher or lower than 1C, eg 0.1C, 0.05C, 0.5C, 5C, or 10C), or 150 mA / g (or more than 150 mA / g Another reference current, high or low, for example 15 mA / g, 7.5 mA / g, 75 mA / g, 750 The first cycle (or another initial cycle, for example, the second cycle, the third cycle, the fourth cycle, the fifth cycle, as measured by cycling at a substantially constant current of A / g, or 1,500 mA / g) Eyes, 6th cycle, 7th cycle, 8th cycle, 9th cycle, or 10th cycle) at least about 50%, at least about 60%, at least about 70%, at least about 75% of the initial or maximum specific capacity, A range of at least about 80%, or at least about 85%, and up to about 90%, up to about 95%, up to about 98% or more is maintained. The stated value for the current may be per unit mass of the positive electrode active material and can be expressed in units of mA / (g of positive electrode active material).

[0119] Further, a battery incorporating an electrolyte comprising a compound of a particular embodiment can span several charge and discharge cycles, for example, 100 cycles after the first cycle, 200 cycles, 300 cycles, 400 cycles. After, 500 cycles, 600 cycles, 1,000 cycles, or even after 5,000 cycles, it can show excellent efficiency maintenance as defined in terms of Coulomb efficiency, and 1C (or another higher or lower than 1C) At a reference rate of, for example, 0.1C, 0.05C, 0.5C, 5C, or 10C), or another reference current higher or lower than 150 mA / g (eg, 150 mA / g) 15 mA / g, 7.5 mA / g, 75 mA / g, 750 mA / g, or 1, 1st cycle (or another initial cycle, eg, 2nd cycle, 3rd cycle, 4th cycle, 5th cycle, 6th cycle, 7th cycle, as measured by cycling at a substantially constant current of 00 mA / g) At least about 70%, at least about 80%, at least about 90%, or at least about 95%, and up to about 97% of the initial or maximum coulomb efficiency in the first, eighth, ninth, or tenth cycle) Up to about 98%, up to about 99%, up to about 99.9%, or beyond. The value described for the current may be per unit mass of the positive electrode active material and can be expressed in units of mA / (g of positive electrode active material).

[0120] With respect to rate performance or output performance, a battery incorporating an electrolyte comprising a compound of certain embodiments maintains a specific capacity (charge and discharge) when charged, discharged, or cycled at a higher rate. Excellent rate performance as defined in terms of both time, so that a high rate of 1C (or another high rate that is n times the reference low rate, n> 1, eg n = 5, low rate at a rate of 0.05C (or another reference rate higher or lower than 0.05C, eg 0.1C), measured at n = 10, n = 20, or n = 100 Or at least about 60%, at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 90%, or at least of the maximum specific capacity About 95%, and up to about 99%, to about 99.5%, to about 99.9%, or a range greater than this, it is maintained. Stated another way, a battery incorporating an electrolyte comprising a compound of a particular embodiment maintains excellent specific capacity (when charged and discharged) when charged, discharged, or cycled at higher currents. ), So that 150 mA / g (or another current that is n times the reference current, n> 1, for example, n = 5, n = 10, n = 20, or n = 100 At a substantially constant current of 7.5 mA / g (or another reference current higher or lower than 7.5 mA / g, eg, 15 mA / g). At least about 60%, at least about 70%, at least about 75%, at least about 80%, at least about 85%, at least about 90%, or at least about 95%, and about 99% of the low rate or maximum specific capacity In up to about 99.5%, to about 99.9%, or a range greater than this, it is maintained. The value described for the current may be per unit mass of the positive electrode active material and can be expressed in units of mA / (g of positive electrode active material).

[0121] Similarly, a battery incorporating an electrolyte comprising a compound of a particular embodiment can exhibit excellent rate performance as defined in terms of maintaining energy density when cycled at a higher rate, resulting in 0.05C measured at a rate of 1C (or another rate that is n times the reference rate, n> 1, for example, n = 5, n = 10, n = 20, or n = 100) (Or another reference rate higher or lower than 0.05C, such as 0.1C) at a low rate or at least about 60%, at least about 70%, at least about 75%, at least about 80% of maximum coulomb efficiency. %, At least about 85%, at least about 90%, or at least about 95%, and up to about 99%, up to about 99.5%, up to about 99.9%, or this Range that exceeds is maintained. Stated another way, a battery incorporating an electrolyte comprising a compound of a particular embodiment can show excellent maintenance of energy density when cycled at higher currents, resulting in 150 mA / g ( Or another current that is n times the reference current, n> 1, eg, n = 5, n = 10, n = 20, or n = 100), measured at a substantially constant current; At least about 60%, at least about 70% of the low rate or maximum coulomb efficiency at a substantially constant current of 5 mA / g (or another reference current higher or lower than 7.5 mA / g, eg, 15 mA / g). %, At least about 75%, at least about 80%, at least about 85%, at least about 90%, or at least about 95%, and up to about 99%, up to about 99.5%, up to about 99.9% Or range is maintained beyond this. The value described for the current may be per unit mass of the positive electrode active material and can be expressed in units of mA / (g of positive electrode active material).

[0122] In addition, a battery incorporating an electrolyte comprising a compound of certain embodiments can have a reduced resistance and reduced resistance increase during cycling. Such resistance reduction results in one or more of the following advantages. (1) Efficient removal of Li ions from the electrode; (2) higher specific capacity and higher energy density; (3) reduced hysteresis in the voltage profile between charge and discharge; and (4) cycling Reducing temperature rise during.

[0123] Advantageously, an electrolyte comprising a compound of a particular embodiment can achieve these performance characteristics over a wide range of operating temperatures (incorporating an electrolyte comprising a compound of a particular embodiment). The battery is about -40 ° C to about 80 ° C, about -40 ° C to about 60 ° C, about -40 ° C to about 25 ° C, about -40 ° C to about 0 ° C, about 0 ° C to about 60 ° C, about 0 ° C. C. to about 25.degree. C., about 25.degree. C. to about 60.degree. C., or other ranges including temperatures above or below 25.degree. C., etc.). The improved electrolyte can also achieve these performance characteristics over a wide range of operating voltages between the rated cut-off voltage and the rated charge voltage (battery is a lithium metal negative electrode (Li / Li ⁺ negative electrode) Measured as about 2V to about 4.2V, about 2V to about 4.3V, about 2V to about 4.5V, about 2V to about 4.6V, about 2V to about 4.7V, about 2V to About 4.95V, about 3V to about 4.2V, about 3V to about 4.3V, about 3V to about 4.5V, about 3V to about 4.6V, about 3V to about 4.7V, about 3V to about 4 .9V, about 2V to about 6V, about 3V to about 6V, about 4.2V to about 6V, about 4.5V to about 6V, about 2V to about 5.5V, about 3V to about 5.5V, about 4. Charge in a voltage range including 5V to about 5.5V, about 2V to about 5V, about 3V to about 5V, about 4.5V to about 5V, or about 5V to about 6V. It is being discharged, or the like when it is cycling). Stated another way, a battery incorporating an electrolyte comprising a compound of a particular embodiment may have another 1C (or higher or lower than 1C) as measured against the negative electrode contained within the battery. By charging at a reference rate, e.g., 0.1C, 0.05C, 0.5C, 5C, or 10C), or another reference current higher or lower than 150 mA / g (or 150 mA / g, e.g., 15 mA / g, 7.5 mA / g, 75 mA / g, 750 mA / g, or 1,500 mA / g) with a substantially constant current charge of at least about 4.2 V, at least about 4.3 V, at least about 4.5V, at least about 4.6V, at least about 4.7V, or at least about 5V, and up to about 5.5V, up to about 6V, or more Having a rated charging voltage of the circumference. The battery can be charged to the rated charge voltage while substantially maintaining the performance characteristics identified above (such as with respect to coulomb efficiency, maintaining specific capacity, maintaining coulomb efficiency, and rate performance).

[0124] With reference to the following formula, a high voltage electrolyte according to some embodiments of the present invention can be formed.
Base electrolyte + stabilizing compound → high voltage electrolyte (1)

[0125] Referring to the following formula, a high temperature electrolyte according to some embodiments of the present invention can be formed.
Base electrolyte + stabilizing compound → high temperature electrolyte (2)

[0126] In formulas (1) and (2), the base electrolyte can include a set of solvents and a set of salts, eg, a set of Li-containing salts in the case of Li-ion batteries. Examples of suitable solvents include carbonates such as ethylene carbonate, dimethyl carbonate, ethyl methyl carbonate, propylene carbonate, methyl propyl carbonate, and diethyl carbonate; sulfones; silanes; nitriles; esters; ethers; Non-aqueous electrolyte solvents for use in Li ion batteries are mentioned. Additional examples of suitable solvents include Xu et al. "Sulfone-based Electrolytes for Lithium-Ion Batteries," Journal of the Electronic Society, 149 (7) A920-A926 (2002); and Nagahamaet. , “High Voltage Performances of Li ₂ NiPO ₄ F Cathode with Distillile-Based Electrolytes,“ Journal of the Electronic Society, 507 ”(details of A6). (Incorporated in the above). Examples of suitable salts include Li-containing salts for use in Li-ion batteries, such as lithium hexafluorophosphate (“LiPF ₆ ”), lithium perchlorate (“LiClO ₄ ”), tetrafluoroboric acid. Lithium (“LiBF ₄ ”), lithium trifluoromethanesulfonate (“LiCF ₃ SO ₃ ”), lithium bis (trifluoromethanesulfonyl) imide (“LiN (CF ₃ SO ₂ ) ₂ ”), lithium bis (perfluoroethylsulfonyl) imide ( _{"LiN (CF 3 CF 2 SO 2} ) 2 "), lithium bis (oxalato) borate ( "LiB (C ₂ O _{4) 2"),} lithium difluoro oxalatoborate ( "LiF ₂ BC ₂ O _4") , And combinations thereof. Other suitable solvents and salts can be used to produce high voltage and high temperature electrolytes with low electronic conductivity, high Li ion solubility, low viscosity, high thermal stability, and other desirable characteristics.

[0127] In formulas (1) and (2), the stabilizing compound is a set of additives that may correspond to a single additive, a pair of different additives, or a combination of three or more different additives It is. Examples of suitable stabilizers include silicon-containing compounds such as silanes, siloxanes, and other organosilicon compounds that contain a SiX ₄ moiety or a SiR ₃ moiety. One or more of the stabilizers described herein can be used in combination with one or more conventional additives to provide improved performance characteristics.

[0128] Examples of suitable silicon-containing compounds include those of the formula

で表されるシランが挙げられる。式（３）において、Ｘ₁、Ｘ₂、Ｘ₃、およびＸ₄は、同一であっても異なっていてもよく、いくつかの実施形態において、Ｘ₁、Ｘ₂、Ｘ₃、およびＸ₄の少なくとも１つは、１〜２０個の炭素原子を含む有機基である。他の実施形態において、Ｘ₁、Ｘ₂、Ｘ₃、およびＸ₄の少なくとも１つは、２０個超の炭素原子を含む有機基である。Ｘ₁、Ｘ₂、Ｘ₃、およびＸ₄は、それぞれ独立に、例えば、水素化物基、ハロ基、ヒドロキシ基、チオ基、アルキル基、アルケニル基、アルキニル基、アリール基、イミニル基、アルコキシ基、アルケノキシ基、アルキノキシ基、アリールオキシ基、カルボキシ基、アルキルカルボニルオキシ基、アルケニルカルボニルオキシ基、アルキニルカルボニルオキシ基、アリールカルボニルオキシ基、アルキルチオ基、アルケニルチオ基、アルキニルチオ基、アリールチオ基、シアノ基、Ｎ−置換アミノ基、アルキルカルボニルアミノ基、Ｎ−置換アルキルカルボニルアミノ基、アルケニルカルボニルアミノ基、Ｎ−置換アルケニルカルボニルアミノ基、アルキニルカルボニルアミノ基、Ｎ−置換アルキニルカルボニルアミノ基、アリールカルボニルアミノ基、Ｎ−置換アリールカルボニルアミノ基、ホウ素含有基、アルミニウム含有基、ケイ素含有基（例えば、シリル基およびシロキシ基）、リン含有基、および硫黄含有基から選択することができる。

The silane represented by these is mentioned. In formula (3), X ₁ , X ₂ , X ₃ , and X ₄ may be the same or different, and in some embodiments, X ₁ , X ₂ , X ₃ , and X ₄ At least one of is an organic group containing 1 to 20 carbon atoms. In other embodiments, at least one of X ₁ , X ₂ , X ₃ , and X ₄ is an organic group containing more than 20 carbon atoms. X ₁ , X ₂ , X ₃ , and X ₄ are each independently, for example, a hydride group, halo group, hydroxy group, thio group, alkyl group, alkenyl group, alkynyl group, aryl group, iminyl group, alkoxy group , Alkenoxy group, alkynoxy group, aryloxy group, carboxy group, alkylcarbonyloxy group, alkenylcarbonyloxy group, alkynylcarbonyloxy group, arylcarbonyloxy group, alkylthio group, alkenylthio group, alkynylthio group, arylthio group, cyano group N-substituted amino group, alkylcarbonylamino group, N-substituted alkylcarbonylamino group, alkenylcarbonylamino group, N-substituted alkenylcarbonylamino group, alkynylcarbonylamino group, N-substituted alkynylcarbonylamino group, arylcarbohydrate Arylamino group, N- substituted arylcarbonylamino group, a boron-containing group, an aluminum-containing group, a silicon-containing group (e.g., silyl group and a siloxy group), may be selected phosphorus-containing group, and a sulfur-containing group.

[0129] Examples of suitable silane compounds include, but are not limited to, 1,2-bis (chlorodimethylsilyl) ethane, bis (trimethylsilylmethyl) sulfide, tetrakis (trimethylsilyl) silane, tetraethylsilane, 4- (trimethylsilyl) ) -3-butyn-2-one, trivinylmethylsilane, dimethyldichlorosilane, hexamethyldisilane, tris (trimethylsilyl) silane, vinyl (trifluoromethyl) dimethylsilane, tetravinylsilane, 1,3-bis [(trimethylsilyl) Ethynyl] benzene, 1,2-bis (methyldifluorosilyl) ethane, 2,2-bis- (trimethylsilyl) dithiane, phenyltrimethoxysilane, pentafluorophenyltriethoxysilane, and combinations thereof. .

[0130] According to certain embodiments, suitable silicon-containing compounds according to formula (3) include those in which at least one of X ₁ , X ₂ , X ₃ , and X ₄ contains a nitrogen atom or group. X ₁ , X ₂ , X ₃ , and X ₄ may be the same or different, and in some embodiments, at least one of X ₁ , X ₂ , X ₃ , and X ₄ is It is an organic group containing 1 to 20 carbon atoms. In other embodiments, at least one of X ₁ , X ₂ , X ₃ , and X ₄ is an organic group containing more than 20 carbon atoms. In some embodiments, at least one of X ₁ , X ₂ , X ₃ , and X ₄ includes an ether linkage, and in other embodiments, at least one of X ₁ , X ₂ , X ₃ , and X ₄ One contains a silicon atom or another heteroatom. X ₁ , X ₂ , X ₃ , and X ₄ are each independently, for example, a hydride group, a hydroxy group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an iminyl group, an alkoxy group, an alkenoxy group, an alkynoxy group , Aryloxy group, carboxy group, alkylcarbonyloxy group, alkenylcarbonyloxy group, alkynylcarbonyloxy group, arylcarbonyloxy group, alkylthio group, alkenylthio group, alkynylthio group, arylthio group, cyano group, N-substituted amino group Alkylcarbonylamino group, N-substituted alkylcarbonylamino group, alkenylcarbonylamino group, N-substituted alkenylcarbonylamino group, alkynylcarbonylamino group, N-substituted alkynylcarbonylamino group, arylcarbonylamino group, N It may be selected substituted aryl carbonyl amino group, and heterocyclic group.

[0131] In certain preferred embodiments, X ₁ , X ₂ , and X ₃ are alkyl groups, particularly methyl groups. In certain preferred embodiments where each of X ₁ , X ₂ , and X ₃ is a methyl group, these silicon-containing compounds are NTMS named after silicon-nitrogen bond (“N”) and trimethylsilyl (“TMS”). Referred to as a compound, wherein each of X ₁ , X ₂ , and X ₃ is a methyl group. As described in more detail below, NTMS compounds exhibit desirable properties as additives according to certain embodiments of the present invention.

[0132] Examples of suitable NTMS compounds include, but are not limited to, bis (trimethylsilyl) carbodiimide, trimethylsilylazide, bis (trimethylsilyl) urea, N, O-bis (trimethylsilyl) trifluoroacetamide, N, O-bis (Trimethylsilyl) acetamide, (N, N-dimethylamino) triethylsilane, methylsilatrane, trimethylsilylisocyanate, tetraisocyanatosilane, 1-trimethylsilyl-1,2,4-triazole, 2- (trimethylsilyl) thiazole, heptamethyldi Silazane, and combinations thereof.

[0133] According to certain embodiments, suitable silicon-containing compounds according to Formula (3) include those in which at least one of X ₁ , X ₂ , X ₃ , and X ₄ contains a carbon atom or group. X ₁ , X ₂ , X ₃ , and X ₄ may be the same or different, and in some embodiments, at least one of X ₁ , X ₂ , X ₃ , and X ₄ is It is an organic group containing 1 to 20 carbon atoms. In other embodiments, at least one of X ₁ , X ₂ , X ₃ , and X ₄ is an organic group containing more than 20 carbon atoms. In some embodiments, at least one of X ₁ , X ₂ , X ₃ , and X ₄ includes an ether linkage, and in other embodiments, at least one of X ₁ , X ₂ , X ₃ , and X ₄ One contains a silicon atom or another heteroatom. X ₁ , X ₂ , X ₃ , and X ₄ are each independently, for example, a hydride group, a hydroxy group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an iminyl group, an alkoxy group, an alkenoxy group, an alkynoxy group , Aryloxy group, carboxy group, alkylcarbonyloxy group, alkenylcarbonyloxy group, alkynylcarbonyloxy group, arylcarbonyloxy group, alkylthio group, alkenylthio group, alkynylthio group, arylthio group, cyano group, N-substituted amino group Alkylcarbonylamino group, N-substituted alkylcarbonylamino group, alkenylcarbonylamino group, N-substituted alkenylcarbonylamino group, alkynylcarbonylamino group, N-substituted alkynylcarbonylamino group, arylcarbonylamino group, N It may be selected substituted aryl carbonyl amino group, and heterocyclic group.

[0134] In certain preferred embodiments, X ₁ , X ₂ , and X ₃ are alkyl groups, particularly methyl groups. In certain preferred embodiments where each of X ₁ , X ₂ , and X ₃ is a methyl group, these silicon-containing compounds are CTMS named after silicon-carbon bonds (“C”) and trimethylsilyl (“TMS”). Referred to as a compound, wherein each of X ₁ , X ₂ , and X ₃ is a methyl group. As described in more detail below, CTMS compounds exhibit desirable properties as additives according to certain embodiments of the invention.

[0135] Examples of suitable CTMS compounds include, but are not limited to, 2- (trimethylsilyl) thiazole, bis (trimethylsilylmethyl) sulfide, 1,3-bis [(trimethylsilyl) ethynyl] benzene, 4- (trimethylsilyl) -3-butyn-2-one, 2,2-bis- (trimethylsilyl) dithiane, and combinations thereof.

[0136] According to certain embodiments, suitable silicon-containing compounds according to formula (3) include those in which at least one of X ₁ , X ₂ , X ₃ , and X ₄ contains a fluorine atom or group. X ₁ , X ₂ , X ₃ , and X ₄ may be the same or different, and in some embodiments, at least one of X ₁ , X ₂ , X ₃ , and X ₄ is It is an organic group containing 1 to 20 carbon atoms. In other embodiments, at least one of X ₁ , X ₂ , X ₃ , and X ₄ is an organic group containing more than 20 carbon atoms. In some embodiments, at least one of X ₁ , X ₂ , X ₃ , and X ₄ includes an ether linkage, and in other embodiments, at least one of X ₁ , X ₂ , X ₃ , and X ₄ One contains a silicon atom or another heteroatom. X ₁ , X ₂ , X ₃ , and X ₄ are each independently, for example, a hydride group, a hydroxy group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an iminyl group, an alkoxy group, an alkenoxy group, an alkynoxy group , Aryloxy group, carboxy group, alkylcarbonyloxy group, alkenylcarbonyloxy group, alkynylcarbonyloxy group, arylcarbonyloxy group, alkylthio group, alkenylthio group, alkynylthio group, arylthio group, cyano group, N-substituted amino group Alkylcarbonylamino group, N-substituted alkylcarbonylamino group, alkenylcarbonylamino group, N-substituted alkenylcarbonylamino group, alkynylcarbonylamino group, N-substituted alkynylcarbonylamino group, arylcarbonylamino group, N It may be selected substituted aryl carbonyl amino group, and heterocyclic group.

[0137] Examples of compounds according to certain embodiments of the present invention (wherein X ₄ includes a fluorine atom or group) include, but are not limited to, tridecafluoro-1,1,2,2-tetrahydrooctyl) Triethoxysilane, 1h, 1h, 2h, 2h-perfluorooctyltriethoxysilane, (pentafluorophenyl) triethoxysilane, bis (1h, 1h, 2h, 2h-perfluorooctyl) tetramethyldisiloxane, 1,3- Bis (heptadecafluoro-1,1,2,2-tetrahydrodecyl) tetramethyldisiloxane, 1,2-bis (methyldifluorosilyl) ethane, 1-3-bis (trifluoropropyl) tetramethyldisiloxane, vinyl (Trifluoromethyl) dimethylsilane, and combinations thereof.

[0138] In certain preferred embodiments, X ₁ , X ₂ , and X ₃ are alkyl groups, particularly methyl groups. In such preferred embodiments where each of R ₁ , R ₂ , and R ₃ is a methyl group, these silicon-containing compounds are referred to as trimethylsilyl (“TMS”) compounds, provided that X ₁ , X ₂ , And each of X ₃ is a methyl group. TMS compounds that also contain fluorine atoms or groups can exhibit desirable properties as additives according to certain embodiments of the invention.

[0139] Examples of suitable TMS compounds (which also contain fluorine atoms or groups) include, but are not limited to, trimethylsilyl trifluoroacetate, N, O-bis (trimethylsilyl) trifluoroacetamide, and combinations thereof Can be mentioned.

[0140] According to certain embodiments, suitable silicon-containing compounds according to formula (3) include those in which at least one of X ₁ , X ₂ , X ₃ , and X ₄ contains an aromatic ring. X ₁ , X ₂ , X ₃ , and X ₄ may be the same or different, and in some embodiments, at least one of X ₁ , X ₂ , X ₃ , and X ₄ is It is an organic group containing 1 to 20 carbon atoms. In other embodiments, at least one of X ₁ , X ₂ , X ₃ , and X ₄ is an organic group containing more than 20 carbon atoms. In some embodiments, at least one of X ₁ , X ₂ , X ₃ , and X ₄ includes an ether linkage, and in other embodiments, at least one of X ₁ , X ₂ , X ₃ , and X ₄ One contains a silicon atom or another heteroatom. X ₁ , X ₂ , X ₃ , and X ₄ are each independently, for example, a hydride group, a hydroxy group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an iminyl group, an alkoxy group, an alkenoxy group, an alkynoxy group , Aryloxy group, carboxy group, alkylcarbonyloxy group, alkenylcarbonyloxy group, alkynylcarbonyloxy group, arylcarbonyloxy group, alkylthio group, alkenylthio group, alkynylthio group, arylthio group, cyano group, N-substituted amino group Alkylcarbonylamino group, N-substituted alkylcarbonylamino group, alkenylcarbonylamino group, N-substituted alkenylcarbonylamino group, alkynylcarbonylamino group, N-substituted alkynylcarbonylamino group, arylcarbonylamino group, N It may be selected substituted aryl carbonyl amino group, and heterocyclic group.

[0141] Examples of compounds according to certain embodiments of the present invention (X ₄ includes an aromatic ring) include, but are not limited to, 1,3-bis [(trimethylsilyl) ethynyl] benzene, phenyltri Mention may be made of methoxysilane, pentafluorophenyltriethoxysilane, and combinations thereof.

[0142] According to certain embodiments, suitable silicon-containing compounds according to formula (3) are those in which at least one of X ₁ , X ₂ , X ₃ , and X ₄ contains one or more unsaturated bonds including. X ₁ , X ₂ , X ₃ , and X ₄ may be the same or different, and in some embodiments, at least one of X ₁ , X ₂ , X ₃ , and X ₄ is It is an organic group containing 1 to 20 carbon atoms. In other embodiments, at least one of X ₁ , X ₂ , X ₃ , and X ₄ is an organic group containing more than 20 carbon atoms. In some embodiments, at least one of X ₁ , X ₂ , X ₃ , and X ₄ includes an ether linkage, and in other embodiments, at least one of X ₁ , X ₂ , X ₃ , and X ₄ One contains a silicon atom or another heteroatom. X ₁ , X ₂ , X ₃ , and X ₄ are each independently, for example, a hydride group, a hydroxy group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an iminyl group, an alkoxy group, an alkenoxy group, an alkynoxy group , Aryloxy group, carboxy group, alkylcarbonyloxy group, alkenylcarbonyloxy group, alkynylcarbonyloxy group, arylcarbonyloxy group, alkylthio group, alkenylthio group, alkynylthio group, arylthio group, cyano group, N-substituted amino group Alkylcarbonylamino group, N-substituted alkylcarbonylamino group, alkenylcarbonylamino group, N-substituted alkenylcarbonylamino group, alkynylcarbonylamino group, N-substituted alkynylcarbonylamino group, arylcarbonylamino group, N It may be selected substituted aryl carbonyl amino group, and heterocyclic group.

[0143] Examples of compounds according to certain embodiments of the present invention (wherein X ₄ includes one or more unsaturated bonds) include, but are not limited to, bis (trimethylsilyl) carbodiimide, tris (trimethylsilyloxy ) Ethylene, isopropenoxytrimethylsilane, 4- (trimethylsilyl) -3-butyn-2-one, trivinylmethylsilane, trivinylmethoxysilane, vinyl (trifluoromethyl) dimethylsilane, bis (trimethylsilyl) itaconate, hexavinyl Disiloxane, trivinylethoxysilane, allyltris (trimethoxysilyloxy) silane, 1,3-bis [(trimethylsilyl) ethynyl] benzene, phenyltrimethoxysilane, pentafluorophenyltriethoxysilane, and combinations thereof. It is.

[0144] According to certain embodiments, suitable silicon-containing compounds according to formula (3) include those in which at least one of X ₁ , X ₂ , X ₃ , and X ₄ contains an oxygen atom or group. X ₁ , X ₂ , X ₃ , and X ₄ may be the same or different, and in some embodiments, at least one of X ₁ , X ₂ , X ₃ , and X ₄ is It is an organic group containing 1 to 20 carbon atoms. In other embodiments, at least one of X ₁ , X ₂ , X ₃ , and X ₄ is an organic group containing more than 20 carbon atoms. In some embodiments, at least one of X ₁ , X ₂ , X ₃ , and X ₄ includes an ether linkage, and in other embodiments, at least one of X ₁ , X ₂ , X ₃ , and X ₄ One contains a silicon atom or another heteroatom. X ₁ , X ₂ , X ₃ , and X ₄ are each independently, for example, a hydride group, a hydroxy group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an iminyl group, an alkoxy group, an alkenoxy group, an alkynoxy group , Aryloxy group, carboxy group, alkylcarbonyloxy group, alkenylcarbonyloxy group, alkynylcarbonyloxy group, arylcarbonyloxy group, alkylthio group, alkenylthio group, alkynylthio group, arylthio group, cyano group, N-substituted amino group Alkylcarbonylamino group, N-substituted alkylcarbonylamino group, alkenylcarbonylamino group, N-substituted alkenylcarbonylamino group, alkynylcarbonylamino group, N-substituted alkynylcarbonylamino group, arylcarbonylamino group, N It may be selected substituted aryl carbonyl amino group, and heterocyclic group.

[0145] Examples of compounds according to certain embodiments of the present invention (wherein X ₄ includes an oxygen atom or group) include, but are not limited to, 1,3-bis (trimethylsiloxy) -1,3- Dimethyldisiloxane, tris (trimethylsilyl) phosphate, decamethyltetrasiloxane, (tridecafluoro-1,1,2,2-tetrahydrooctyl) triethoxysilane, trimethylsilyl trifluoroacetate, tris (trimethylsilyloxy) silane, silicon tetraacetate , Tetramethylorthosilicate, decamethylcyclopentasiloxane, tris (trimethylsilyloxy) ethylene, ethoxytrimethylsilane, octakis (dimethylsiloxy) -t8-silsesquioxane, isopropenoxytrimethylsilane, hexamethyl Siloxane, phenyltrimethoxysilane, pentafluorophenyltriethoxysilane, hexamethylcyclotrisiloxane, tris (trimethylsilyl) phosphite, N, O-bis (trimethylsilyl) acetamide, tris (trimethylsilyl) borate, tetrakis (trimethylsilyloxy) silane, Tetrakis (dimethylsilyloxy) silane, bis (tridecafluoro-1,1,2,2-tetrahydrooctyl) tetramethyldisiloxane, (cyclohexenyloxy) trimethylsilane, mono- (trimethylsilyl) phosphite, 2- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, trimethyl-n-propoxysilane, methoxytrimethylsilane, tetrakis (trimethylsiloxy) titanium, bis Trimethoxysilylpropyl) urea, 1,3-bis (trifluoropropyl) tetramethyldisiloxane, methacryloxypropylsilatrane, triethoxysilylundecanol ethylene glycol acetal, tris (trimethylsiloxy) antimony, trivinylmethoxysilane, Tetradecamethylhexasiloxane, methyltris (trimethylsiloxy) silane, dodecamethylcyclohexasiloxane, bis (trimethylsilyl) itaconate, methylsilatrane, hexavinyldisiloxane, 3-ethylheptamethyltrisiloxane, 1,3-bis (heptadeca Fluoro-1,1,2,2-tetrahydrodecyl) tetramethyldisiloxane, trivinylethoxysilane, 1,1,1,3,3-pentamethyl-3-acetoxydishiro Xan, bis (trimethylsilyl) adipate, allyltris (trimethoxysilyloxy) silane, trimethylsilylpolyphosphate, dodecamethylcyclohexasiloxane, and combinations thereof.

[0146] In certain preferred embodiments, X ₁ , X ₂ , and X ₃ are alkyl groups, particularly methyl groups. In such preferred embodiments in which each of X ₁ , X ₂ , and X ₃ is a methyl group, these silicon-containing compounds are named after silicon-oxygen bonds (“O”) and trimethylsilyl (“TMS”). It is referred to as an OTMS compound, where each of X ₁ , X ₂ , and X ₃ is a methyl group. As described in more detail below, OTMS compounds exhibit desirable properties as additives according to certain embodiments of the invention.

[0147] Examples of suitable OTMS compounds include, but are not limited to, 1,3-bis (trimethylsiloxy) -1,3-dimethyldisiloxane, decamethyltetrasiloxane, trimethylsilyl trifluoroacetate, ethoxytrimethylsilane, Isopropenoxytrimethylsilane, hexamethyldisiloxane, tris (trimethylsilyl) phosphate, tris (trimethylsilyl) phosphite, tetrakis (trimethylsilyloxy) silane, tetrakis (trimethylsilyloxy) silane, tris (dimethylsilyloxy) ethylene, N, O- Bis (trimethylsilyl) acetamide, tris (trimethylsilyl) borate, bis (tridecafluoro-1,1,2,2-tetrahydrooctyl) tetramethyldisiloxane, tri Til-n-propoxysilane, (cyclohexenyloxy) trimethylsilane, mono- (trimethylsilyl) phosphite, methoxytrimethylsilane, tetrakis (trimethylsiloxy) titanium, 1,3-bis (trifluoropropyl) tetramethyldisiloxane, tris (Trimethylsiloxy) antimony, trivinylmethoxysilane, tetradecamethylhexasiloxane, methyltris (trimethylsiloxy) silane, dodecamethylcyclohexasiloxane, bis (trimethylsilyl) itaconate, 3-ethylheptamethyltrisiloxane, 1,3-bis ( Heptadecafluoro-1,1,2,2-tetrahydrodecyl) tetramethyldisiloxane, 1,1,1,3,3-pentamethyl-3-acetoxydisiloxane, bis (trimethyl) Rusilyl) adipate, allyltris (trimethoxysilyloxy) silane, trimethylsilylpolyphosphate, and combinations thereof.

[0148] Desirable performance characteristics can be obtained by including at least one A and at least one silicon-A bond in the silane according to formula (3), where A is a carbon atom or a heteroatom such as boron, One selected from aluminum, silicon, phosphorus, sulfur, fluorine, chlorine, bromine and iodine atoms. For example, X _1, X _2, X _3, and at least one of X ₄ may include an A to be bonded to the silicon of the formula _{(3), X 1, X} 2, X 3, and X ₄ The remaining one is, for example, each independently a hydride group, a hydroxy group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an iminyl group, an alkoxy group, an alkenoxy group, an alkynoxy group, an aryloxy group, a carboxy group, Alkylcarbonyloxy group, alkenylcarbonyloxy group, alkynylcarbonyloxy group, arylcarbonyloxy group, alkylthio group, alkenylthio group, alkynylthio group, arylthio group, cyano group, N-substituted amino group, alkylcarbonylamino group, N- Substituted alkylcarbonylamino, alkenylcarbonylamino, N-substituted alkenyl It can be selected from a bonylamino group, an alkynylcarbonylamino group, an N-substituted alkynylcarbonylamino group, an arylcarbonylamino group, and an N-substituted arylcarbonylamino group. A plurality of X ₁ , X ₂ , X ₃ , and X _{4 wherein} the silane according to formula (3) can include a plurality of silicon-A bonds, such as in the range of 2-4 or 3-4. Thus, it is believed that each can contain A bonded to silicon of formula (3). A plurality of X ₁ , X ₂ , X ₃ , and X ₄ is a plurality of silicon-A bonds (with respect to different A) such that the silane according to formula (3) ranges from 2 to 4 or 3 to 4 It is also contemplated that each different A bonded to the silicon of formula (3) can be included. The number of silicon-A bonds can be increased beyond 4, for example by including silicon and silicon-A bonds in one or more of X ₁ , X ₂ , X ₃ , and X _4. .

[0149] Desirable performance characteristics can also be obtained by including at least one A and at least one silicon-O-A bond in the silane according to formula (3), where O is oxygen and A is carbon. Those selected from atoms or heteroatoms such as boron, aluminum, silicon, phosphorus, and sulfur atoms. For example, at least one of X ₁ , X ₂ , X ₃ , and X ₄ can comprise OA bonded to silicon of formula (3) via a silicon-OA bond, and X ₁ , X ₂ , X ₃ , and X ₄ are each independently, for example, hydride group, hydroxy group, alkyl group, alkenyl group, alkynyl group, aryl group, iminyl group, alkoxy group, alkenoxy group , Alkynoxy group, aryloxy group, carboxy group, alkylcarbonyloxy group, alkenylcarbonyloxy group, alkynylcarbonyloxy group, arylcarbonyloxy group, alkylthio group, alkenylthio group, alkynylthio group, arylthio group, cyano group, N- Substituted amino group, alkylcarbonylamino group, N-substituted alkylcarbonylamino group, alkenylcarbonyl group It can be selected from a mino group, an N-substituted alkenylcarbonylamino group, an alkynylcarbonylamino group, an N-substituted alkynylcarbonylamino group, an arylcarbonylamino group, and an N-substituted arylcarbonylamino group. A plurality of X ₁ , X ₂ , X ₃ , and X ₄ are such that the silane according to formula (3) contains a plurality of silicon-O—A bonds such as in the range of 2-4 or 3-4. It is believed that each can contain OA bonded to silicon of formula (3) via a silicon-OA bond. A plurality of X ₁ , X ₂ , X ₃ , and X ₄ are those wherein the silane according to formula (3) has a plurality of silicon-O—A bonds (different A It is also contemplated that each different A bonded to the silicon of formula (3) via an oxygen atom can be included. The number of silicon-O-A bonds exceeds 4 by including, for example, silicon, oxygen, and silicon-O-A bonds within one or more of X ₁ , X ₂ , X ₃ , and X _4. Can be increased.

[0150] When A is boron, specific examples of silicon-containing compounds according to formula (3) include:

で表されるケイ素含有ボランが挙げられる。
式（４）〜（７）において、Ｒ₁、Ｒ₂、およびＲ₃は、式（３）によるＸ₁、Ｘ₂、およびＸ₃に相当し得る。Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀、およびＲ₁₁は、同一であっても異なっていてもよく、いくつかの実施形態において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀、およびＲ₁₁の少なくとも１つは、１〜２０個の炭素原子を含む有機基である。他の実施形態において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀、およびＲ₁₁の少なくとも１つは、２０個超の炭素原子を含む有機基である。いくつかの実施形態において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀、およびＲ₁₁の少なくとも１つは、エーテル結合を含み、他の実施形態において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀、およびＲ₁₁の少なくとも１つは、ケイ素原子または別のヘテロ原子を含む。Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀、およびＲ₁₁は、例えば、それぞれ独立に、水素化物基、ヒドロキシ基、アルキル基、アルケニル基、アルキニル基、アリール基、イミニル基、アルコキシ基、アルケノキシ基、アルキノキシ基、アリールオキシ基、カルボキシ基、アルキルカルボニルオキシ基、アルケニルカルボニルオキシ基、アルキニルカルボニルオキシ基、アリールカルボニルオキシ基、アルキルチオ基、アルケニルチオ基、アルキニルチオ基、アリールチオ基、シアノ基、Ｎ−置換アミノ基、アルキルカルボニルアミノ基、Ｎ−置換アルキルカルボニルアミノ基、アルケニルカルボニルアミノ基、Ｎ−置換アルケニルカルボニルアミノ基、アルキニルカルボニルアミノ基、Ｎ−置換アルキニルカルボニルアミノ基、アリールカルボニルアミノ基、およびＮ−置換アリールカルボニルアミノ基から選択することができる。式（７）において、Ｒ₁₂は、いくつかの実施形態において、１〜２０個の炭素原子を含む２価の有機基であり、他の実施形態において、Ｒ₁₂は、２０個超の炭素原子を含む２価の有機基である。Ｒ₁₂は、例えば、アルキレン基、アルケニレン基、およびアルキニレン基から選択することができる。

The silicon-containing borane represented by these is mentioned.
In formulas (4) to (7), R ₁ , R ₂ , and R ₃ may correspond to X ₁ , X ₂ , and X ₃ according to formula (3). R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , and R ₁₁ may be the same or different, and some implementations In embodiments, at _{least one} of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , and R ₁₁ has 1 to 20 carbon atoms. Contains organic groups. In other embodiments, at _{least one} of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , and R ₁₁ is greater than 20 carbons. An organic group containing an atom. In some embodiments, at _{least one} of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , and R ₁₁ includes an ether linkage. In other embodiments, at _{least one} of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , and R ₁₁ is a silicon atom or another Of heteroatoms. R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , and R ₁₁ are each independently, for example, a hydride group, a hydroxy group, or an alkyl group. Alkenyl group, alkynyl group, aryl group, iminyl group, alkoxy group, alkenoxy group, alkynoxy group, aryloxy group, carboxy group, alkylcarbonyloxy group, alkenylcarbonyloxy group, alkynylcarbonyloxy group, arylcarbonyloxy group, alkylthio Group, alkenylthio group, alkynylthio group, arylthio group, cyano group, N-substituted amino group, alkylcarbonylamino group, N-substituted alkylcarbonylamino group, alkenylcarbonylamino group, N-substituted alkenylcarbonylamino group, alkynylcarbonyl Amino group, N-substituted alkynylcarbonyl It can be selected from a ruamino group, an arylcarbonylamino group, and an N-substituted arylcarbonylamino group. In formula (7), R ₁₂ is a divalent organic group containing 1-20 carbon atoms in some embodiments, and in other embodiments R ₁₂ is greater than 20 carbon atoms. Is a divalent organic group. R ₁₂ can be selected from, for example, an alkylene group, an alkenylene group, and an alkynylene group.

[0151] When A is aluminum, specific examples of silicon-containing compounds according to formula (3) include:

で表されるものが挙げられる。式（８）〜（１１）において、Ｒ₁、Ｒ₂、およびＲ₃は、式（３）によるＸ₁、Ｘ₂、およびＸ₃に相当し得る。Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀、およびＲ₁₁は、同一であっても異なっていてもよく、いくつかの実施形態において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀、およびＲ₁₁の少なくとも１つは、１〜２０個の炭素原子を含む有機基である。他の実施形態において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀、およびＲ₁₁の少なくとも１つは、２０個超の炭素原子を含む有機基である。いくつかの実施形態において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀、およびＲ₁₁の少なくとも１つは、エーテル結合を含み、他の実施形態において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀、およびＲ₁₁の少なくとも１つは、ケイ素原子または別のヘテロ原子を含む。Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀、およびＲ₁₁は、例えば、それぞれ独立に、水素化物基、ヒドロキシ基、アルキル基、アルケニル基、アルキニル基、アリール基、イミニル基、アルコキシ基、アルケノキシ基、アルキノキシ基、アリールオキシ基、カルボキシ基、アルキルカルボニルオキシ基、アルケニルカルボニルオキシ基、アルキニルカルボニルオキシ基、アリールカルボニルオキシ基、アルキルチオ基、アルケニルチオ基、アルキニルチオ基、アリールチオ基、シアノ基、Ｎ−置換アミノ基、アルキルカルボニルアミノ基、Ｎ−置換アルキルカルボニルアミノ基、アルケニルカルボニルアミノ基、Ｎ−置換アルケニルカルボニルアミノ基、アルキニルカルボニルアミノ基、Ｎ−置換アルキニルカルボニルアミノ基、アリールカルボニルアミノ基、およびＮ−置換アリールカルボニルアミノ基から選択することができる。式（１１）において、Ｒ₁₂は、いくつかの実施形態において、１〜２０個の炭素原子を含む２価の有機基であり、他の実施形態において、Ｒ₁₂は、２０個超の炭素原子を含む２価の有機基である。Ｒ₁₂は、例えば、アルキレン基、アルケニレン基、およびアルキニレン基から選択することができる。

The thing represented by is mentioned. In formulas (8)-(11), R ₁ , R ₂ , and R ₃ may correspond to X ₁ , X ₂ , and X ₃ according to formula (3). R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , and R ₁₁ may be the same or different, and some implementations In embodiments, at _{least one} of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , and R ₁₁ has 1 to 20 carbon atoms. Contains organic groups. In other embodiments, at _{least one} of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , and R ₁₁ is greater than 20 carbons. An organic group containing an atom. In some embodiments, at _{least one} of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , and R ₁₁ includes an ether linkage. In other embodiments, at _{least one} of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , and R ₁₁ is a silicon atom or another Of heteroatoms. R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , and R ₁₁ are each independently, for example, a hydride group, a hydroxy group, or an alkyl group. Alkenyl group, alkynyl group, aryl group, iminyl group, alkoxy group, alkenoxy group, alkynoxy group, aryloxy group, carboxy group, alkylcarbonyloxy group, alkenylcarbonyloxy group, alkynylcarbonyloxy group, arylcarbonyloxy group, alkylthio Group, alkenylthio group, alkynylthio group, arylthio group, cyano group, N-substituted amino group, alkylcarbonylamino group, N-substituted alkylcarbonylamino group, alkenylcarbonylamino group, N-substituted alkenylcarbonylamino group, alkynylcarbonyl Amino group, N-substituted alkynylcarbonyl It can be selected from a ruamino group, an arylcarbonylamino group, and an N-substituted arylcarbonylamino group. In formula (11), R ₁₂ is, in some embodiments, a divalent organic group containing 1-20 carbon atoms, and in other embodiments, R ₁₂ is greater than 20 carbon atoms. Is a divalent organic group. R ₁₂ can be selected from, for example, an alkylene group, an alkenylene group, and an alkynylene group.

[0152] When A is carbon, specific examples of silicon-containing compounds according to formula (3) include:

で表されるものが挙げられる。式（１２）〜（１７）において、Ｒ₁、Ｒ₂、およびＲ₃は、式（３）によるＸ₁、Ｘ₂、およびＸ₃に相当し得る。Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀、Ｒ₁₁、Ｒ₁₂、Ｒ₁₃、Ｒ₁₄、およびＲ₁₅は、同一であっても異なっていてもよく、いくつかの実施形態において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀、Ｒ₁₁、Ｒ₁₂、Ｒ₁₃、Ｒ₁₄、およびＲ₁₅の少なくとも１つは、１〜２０個の炭素原子を含む有機基である。他の実施形態において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀、Ｒ₁₁、Ｒ₁₂、Ｒ₁₃、Ｒ₁₄、およびＲ₁₅の少なくとも１つは、２０個超の炭素原子を含む有機基である。いくつかの実施形態において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀、Ｒ₁₁、Ｒ₁₂、Ｒ₁₃、Ｒ₁₄、およびＲ₁₅の少なくとも１つは、エーテル結合を含み、他の実施形態において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀、Ｒ₁₁、Ｒ₁₂、Ｒ₁₃、Ｒ₁₄、およびＲ₁₅の少なくとも１つは、ケイ素原子または別のヘテロ原子を含む。Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀、Ｒ₁₁、Ｒ₁₂、Ｒ₁₃、Ｒ₁₄、およびＲ₁₅は、例えば、それぞれ独立に、水素化物基、ヒドロキシ基、アルキル基、アルケニル基、アルキニル基、アリール基、イミニル基、アルコキシ基、アルケノキシ基、アルキノキシ基、アリールオキシ基、カルボキシ基、アルキルカルボニルオキシ基、アルケニルカルボニルオキシ基、アルキニルカルボニルオキシ基、アリールカルボニルオキシ基、アルキルチオ基、アルケニルチオ基、アルキニルチオ基、アリールチオ基、シアノ基、Ｎ−置換アミノ基、アルキルカルボニルアミノ基、Ｎ−置換アルキルカルボニルアミノ基、アルケニルカルボニルアミノ基、Ｎ−置換アルケニルカルボニルアミノ基、アルキニルカルボニルアミノ基、Ｎ−置換アルキニルカルボニルアミノ基、アリールカルボニルアミノ基、およびＮ−置換アリールカルボニルアミノ基から選択することができる。式（１６）および（１７）において、Ｒ₁₆は、いくつかの実施形態において、１〜２０個の炭素原子を含む２価の有機基であり、他の実施形態において、Ｒ₁₆は、２０個超の炭素原子を含む２価の有機基である。Ｒ₁₆は、例えば、アルキレン基、アルケニレン基、およびアルキニレン基から選択することができる。

The thing represented by is mentioned. In formulas (12)-(17), R ₁ , R ₂ , and R ₃ may correspond to X ₁ , X ₂ , and X ₃ according to formula (3). R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , and R ₁₅ are the same. In some embodiments, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ in some embodiments. , R ₁₃ , R ₁₄ , and R ₁₅ are organic groups containing 1 to 20 carbon atoms. In other embodiments, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , and R _At least one of ₁₅ is an organic group containing more than 20 carbon atoms. In some embodiments, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , and _At least one of R ₁₅ includes an ether bond, and in other embodiments R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R _At least one of ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , and R ₁₅ contains a silicon atom or another heteroatom. R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , and R ₁₅ are, for example, Independently, hydride group, hydroxy group, alkyl group, alkenyl group, alkynyl group, aryl group, iminyl group, alkoxy group, alkenoxy group, alkynoxy group, aryloxy group, carboxy group, alkylcarbonyloxy group, alkenylcarbonyloxy group , Alkynylcarbonyloxy group, arylcarbonyloxy group, alkylthio group, alkenylthio group, alkynylthio group, arylthio group, cyano group, N-substituted amino group, alkylcarbonylamino group, N-substituted alkylcarbonylamino group, alkenylcarbonylamino Group, N-substituted alkenylcarbonylamino group, alkynylcarbonylamino group N- substituted alkynylcarbonyl amino group, can be selected arylcarbonylamino group, and N- substituted arylcarbonylamino group. In formulas (16) and (17), R ₁₆ is, in some embodiments, a divalent organic group containing 1-20 carbon atoms, and in other embodiments, R ₁₆ is 20 It is a divalent organic group containing a super carbon atom. R ₁₆ can be selected from, for example, an alkylene group, an alkenylene group, and an alkynylene group.

[0153] When A is carbon, further examples of silicon-containing compounds according to formula (3) include:

で表されるものが挙げられる。式（１８）および（１９）において、Ｒ₁、Ｒ₂、およびＲ₃は、式（３）によるＸ₁、Ｘ₂、およびＸ₃に相当し得る。Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、およびＲ₇は、同一であっても異なっていてもよく、いくつかの実施形態において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、およびＲ₇の少なくとも１つは、１〜２０個の炭素原子を含む有機基である。他の実施形態において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、およびＲ₇の少なくとも１つは、２０個超の炭素原子を含む有機基である。いくつかの実施形態において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、およびＲ₇の少なくとも１つは、エーテル結合を含み、他の実施形態において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、およびＲ₇の少なくとも１つは、ケイ素原子または別のヘテロ原子を含む。Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、およびＲ₇は、例えば、それぞれ独立に、水素化物基、ヒドロキシ基、アルキル基、アルケニル基、アルキニル基、アリール基、イミニル基、アルコキシ基、アルケノキシ基、アルキノキシ基、アリールオキシ基、カルボキシ基、アルキルカルボニルオキシ基、アルケニルカルボニルオキシ基、アルキニルカルボニルオキシ基、アリールカルボニルオキシ基、アルキルチオ基、アルケニルチオ基、アルキニルチオ基、アリールチオ基、シアノ基、Ｎ−置換アミノ基、アルキルカルボニルアミノ基、Ｎ−置換アルキルカルボニルアミノ基、アルケニルカルボニルアミノ基、Ｎ−置換アルケニルカルボニルアミノ基、アルキニルカルボニルアミノ基、Ｎ−置換アルキニルカルボニルアミノ基、アリールカルボニルアミノ基、およびＮ−置換アリールカルボニルアミノ基から選択することができる。
いくつかの実施形態において、Ｒ₇は、形態−ＣＯ−の任意のカルボニル基を含まず、他の実施形態において、Ｒ₇は、形態−ＳＯ₂−の任意のスルホニル基を含まない。

The thing represented by is mentioned. In formulas (18) and (19), R ₁ , R ₂ , and R ₃ may correspond to X ₁ , X ₂ , and X ₃ according to formula (3). R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , and R ₇ may be the same or different, and in some embodiments, R ₁ , R ₂ , R ₃ , At least one of R ₄ , R ₅ , R ₆ , and R ₇ is an organic group containing 1 to 20 carbon atoms. In other embodiments, at least one of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , and R ₇ is an organic group containing more than 20 carbon atoms. In some embodiments, at least one of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , and R ₇ includes an ether linkage, and in other embodiments, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , and R ₇ contain a silicon atom or another heteroatom. R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , and R ₇ are each independently, for example, a hydride group, a hydroxy group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an iminyl group , Alkoxy group, alkenoxy group, alkynoxy group, aryloxy group, carboxy group, alkylcarbonyloxy group, alkenylcarbonyloxy group, alkynylcarbonyloxy group, arylcarbonyloxy group, alkylthio group, alkenylthio group, alkynylthio group, arylthio group Cyano group, N-substituted amino group, alkylcarbonylamino group, N-substituted alkylcarbonylamino group, alkenylcarbonylamino group, N-substituted alkenylcarbonylamino group, alkynylcarbonylamino group, N-substituted alkynylcarbonylamino group, arylcal It may be selected from Niruamino group, and N- substituted arylcarbonylamino group.
In some embodiments, R ₇ does not include any carbonyl group of the form —CO—, and in other embodiments R ₇ does not include any sulfonyl group of the form —SO ₂ —.

[0154] In certain preferred embodiments, the compound alkyl group of formula (19) comprises R ₁ , R ₂ , and R ₃ . In some embodiments, R ₁ , R ₂ , and R ₃ are methyl groups. Examples of such trimethylsilyl compounds (R ₇ is selected such that the compound comprises an ester) include, but are not limited to, silicon tetraacetate, bis (trimethylsilyl) itaconate, bis (trimethylsilyl) adipate, 1 , 1,1,3,3-pentamethyl-3-acetoxydisiloxane, trimethylsilyl trifluoroacetate, and combinations thereof.

[0155] When A is silicon, specific examples of silicon-containing compounds according to formula (3) include:

で表されるシランが挙げられる。式（２０）〜（２５）において、Ｒ₁、Ｒ₂、およびＲ₃は、式（３）によるＸ₁、Ｘ₂、およびＸ₃に相当し得る。Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀、Ｒ₁₁、Ｒ₁₂、Ｒ₁₃、Ｒ₁₄、およびＲ₁₅は、同一であっても異なっていてもよく、いくつかの実施形態において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀、Ｒ₁₁、Ｒ₁₂、Ｒ₁₃、Ｒ₁₄、およびＲ₁₅の少なくとも１つは、１〜２０個の炭素原子を含む有機基である。他の実施形態において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀、Ｒ₁₁、Ｒ₁₂、Ｒ₁₃、Ｒ₁₄、およびＲ₁₅の少なくとも１つは、２０個超の炭素原子を含む有機基である。いくつかの実施形態において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀、Ｒ₁₁、Ｒ₁₂、Ｒ₁₃、Ｒ₁₄、およびＲ₁₅の少なくとも１つは、エーテル結合を含み、他の実施形態において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀、Ｒ₁₁、Ｒ₁₂、Ｒ₁₃、Ｒ₁₄、およびＲ₁₅の少なくとも１つは、ケイ素原子または別のヘテロ原子を含む。Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀、Ｒ₁₁、Ｒ₁₂、Ｒ₁₃、Ｒ₁₄、およびＲ₁₅は、例えば、それぞれ独立に、水素化物基、ヒドロキシ基、アルキル基、アルケニル基、アルキニル基、アリール基、イミニル基、アルコキシ基、アルケノキシ基、アルキノキシ基、アリールオキシ基、カルボキシ基、アルキルカルボニルオキシ基、アルケニルカルボニルオキシ基、アルキニルカルボニルオキシ基、アリールカルボニルオキシ基、アルキルチオ基、アルケニルチオ基、アルキニルチオ基、アリールチオ基、シアノ基、Ｎ−置換アミノ基、アルキルカルボニルアミノ基、Ｎ−置換アルキルカルボニルアミノ基、アルケニルカルボニルアミノ基、Ｎ−置換アルケニルカルボニルアミノ基、アルキニルカルボニルアミノ基、Ｎ−置換アルキニルカルボニルアミノ基、アリールカルボニルアミノ基、およびＮ−置換アリールカルボニルアミノ基から選択することができる。式（２４）および（２５）において、Ｒ₁₆は、いくつかの実施形態において、１〜２０個の炭素原子を含む２価の有機基であり、他の実施形態において、Ｒ₁₆は、２０個超の炭素原子を含む２価の有機基である。Ｒ₁₆は、例えば、アルキレン基、アルケニレン基、およびアルキニレン基から選択することができる。いくつかの実施形態において、式（２０）〜（２５）によるシランは、非ポリマーであり、約１０，０００ダルトン以下、例えば、約５，０００ダルトン以下、約４，０００ダルトン以下、約３，０００ダルトン以下、約２，０００ダルトン以下、約１，０００ダルトン以下、約９００ダルトン以下、約８００ダルトン以下、約７００ダルトン以下、約６００ダルトン以下、または約５００ダルトン以下の分子量を有する。

The silane represented by these is mentioned. In formulas (20)-(25), R ₁ , R ₂ , and R ₃ may correspond to X ₁ , X ₂ , and X ₃ according to formula (3). R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , and R ₁₅ are the same. In some embodiments, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ in some embodiments. , R ₁₃ , R ₁₄ , and R ₁₅ are organic groups containing 1 to 20 carbon atoms. In other embodiments, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , and R _At least one of ₁₅ is an organic group containing more than 20 carbon atoms. In some embodiments, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , and _At least one of R ₁₅ includes an ether bond, and in other embodiments R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R _At least one of ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , and R ₁₅ contains a silicon atom or another heteroatom. R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , and R ₁₅ are, for example, Independently, hydride group, hydroxy group, alkyl group, alkenyl group, alkynyl group, aryl group, iminyl group, alkoxy group, alkenoxy group, alkynoxy group, aryloxy group, carboxy group, alkylcarbonyloxy group, alkenylcarbonyloxy group , Alkynylcarbonyloxy group, arylcarbonyloxy group, alkylthio group, alkenylthio group, alkynylthio group, arylthio group, cyano group, N-substituted amino group, alkylcarbonylamino group, N-substituted alkylcarbonylamino group, alkenylcarbonylamino Group, N-substituted alkenylcarbonylamino group, alkynylcarbonylamino group N- substituted alkynylcarbonyl amino group, can be selected arylcarbonylamino group, and N- substituted arylcarbonylamino group. In formulas (24) and (25), R ₁₆ is, in some embodiments, a divalent organic group containing 1-20 carbon atoms, and in other embodiments, R ₁₆ is 20 It is a divalent organic group containing a super carbon atom. R ₁₆ can be selected from, for example, an alkylene group, an alkenylene group, and an alkynylene group. In some embodiments, the silanes according to formulas (20)-(25) are non-polymeric and are about 10,000 daltons or less, such as about 5,000 daltons or less, about 4,000 daltons or less, about 3, It has a molecular weight of no more than 000 daltons, no more than about 2,000 daltons, no more than about 1,000 daltons, no more than about 900 daltons, no more than about 800 daltons, no more than about 700 daltons, no more than about 600 daltons, or no more than about 500 daltons.

[0156] Examples of compounds according to certain embodiments of the present invention (A is silicon) include, but are not limited to, decamethylcyclopentasiloxane, octakis (dimethylsiloxy) -t8-silsesquioxane , Hexamethylcyclotrisiloxane, octaphenyl-t8-silsesquioxane, dodecamethylcyclohexasiloxane, and combinations thereof.

[0157] When A is phosphorus, specific examples of silicon-containing compounds according to formula (3) include:

で表されるホスフィンが挙げられる。式（２６）〜（２９）において、Ｒ₁、Ｒ₂、およびＲ₃は、式（３）によるＸ₁、Ｘ₂、およびＸ₃に相当し得る。Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀、およびＲ₁₁は、同一であっても異なっていてもよく、いくつかの実施形態において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀、およびＲ₁₁の少なくとも１つは、１〜２０個の炭素原子を含む有機基である。他の実施形態において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀、およびＲ₁₁の少なくとも１つは、２０個超の炭素原子を含む有機基である。いくつかの実施形態において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀、およびＲ₁₁の少なくとも１つは、エーテル結合を含み、他の実施形態において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀、およびＲ₁₁の少なくとも１つは、ケイ素原子または別のヘテロ原子を含む。Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀、およびＲ₁₁は、例えば、それぞれ独立に、水素化物基、ヒドロキシ基、アルキル基、アルケニル基、アルキニル基、アリール基、イミニル基、アルコキシ基、アルケノキシ基、アルキノキシ基、アリールオキシ基、カルボキシ基、アルキルカルボニルオキシ基、アルケニルカルボニルオキシ基、アルキニルカルボニルオキシ基、アリールカルボニルオキシ基、アルキルチオ基、アルケニルチオ基、アルキニルチオ基、アリールチオ基、シアノ基、Ｎ−置換アミノ基、アルキルカルボニルアミノ基、Ｎ−置換アルキルカルボニルアミノ基、アルケニルカルボニルアミノ基、Ｎ−置換アルケニルカルボニルアミノ基、アルキニルカルボニルアミノ基、Ｎ−置換アルキニルカルボニルアミノ基、アリールカルボニルアミノ基、およびＮ−置換アリールカルボニルアミノ基から選択することができる。式（２９）において、Ｒ₁₂は、いくつかの実施形態において、１〜２０個の炭素原子を含む２価の有機基であり、他の実施形態において、Ｒ₁₂は、２０個超の炭素原子を含む２価の有機基である。Ｒ₁₂は、例えば、アルキレン基、アルケニレン基、およびアルキニレン基から選択することができる。

The phosphine represented by these is mentioned. In formulas (26) to (29), R ₁ , R ₂ , and R ₃ may correspond to X ₁ , X ₂ , and X ₃ according to formula (3). R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , and R ₁₁ may be the same or different, and some implementations In embodiments, at _{least one} of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , and R ₁₁ has 1 to 20 carbon atoms. Contains organic groups. In other embodiments, at _{least one} of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , and R ₁₁ is greater than 20 carbons. An organic group containing an atom. In some embodiments, at _{least one} of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , and R ₁₁ includes an ether linkage. In other embodiments, at _{least one} of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , and R ₁₁ is a silicon atom or another Of heteroatoms. R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , and R ₁₁ are each independently, for example, a hydride group, a hydroxy group, or an alkyl group. Alkenyl group, alkynyl group, aryl group, iminyl group, alkoxy group, alkenoxy group, alkynoxy group, aryloxy group, carboxy group, alkylcarbonyloxy group, alkenylcarbonyloxy group, alkynylcarbonyloxy group, arylcarbonyloxy group, alkylthio Group, alkenylthio group, alkynylthio group, arylthio group, cyano group, N-substituted amino group, alkylcarbonylamino group, N-substituted alkylcarbonylamino group, alkenylcarbonylamino group, N-substituted alkenylcarbonylamino group, alkynylcarbonyl Amino group, N-substituted alkynylcarbonyl It can be selected from a ruamino group, an arylcarbonylamino group, and an N-substituted arylcarbonylamino group. In formula (29), R ₁₂ is, in some embodiments, a divalent organic group containing 1-20 carbon atoms, and in other embodiments, R ₁₂ is greater than 20 carbon atoms. Is a divalent organic group. R ₁₂ can be selected from, for example, an alkylene group, an alkenylene group, and an alkynylene group.

[0158] When A is phosphorus, further examples of silicon-containing compounds according to formula (3) include:

で表されるホスホランが挙げられる。式（３０）〜（３７）において、Ｒ₁、Ｒ₂、およびＲ₃は、式（３）によるＸ₁、Ｘ₂、およびＸ₃に相当し得る。Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀、Ｒ₁₁、Ｒ₁₂、Ｒ₁₃、Ｒ₁₄、Ｒ₁₅、Ｒ₁₆、Ｒ₁₇、Ｒ₁₈、およびＲ₁₉は、同一であっても異なっていてもよく、いくつかの実施形態において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀、Ｒ₁₁、Ｒ₁₂、Ｒ₁₃、Ｒ₁₄、Ｒ₁₅、Ｒ₁₆、Ｒ₁₇、Ｒ₁₈、およびＲ₁₉の少なくとも１つは、１〜２０個の炭素原子を含む有機基である。他の実施形態において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀、Ｒ₁₁、Ｒ₁₂、Ｒ₁₃、Ｒ₁₄、Ｒ₁₅、Ｒ₁₆、Ｒ₁₇、Ｒ₁₈、およびＲ₁₉の少なくとも１つは、２０個超の炭素原子を含む有機基である。いくつかの実施形態において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀、Ｒ₁₁、Ｒ₁₂、Ｒ₁₃、Ｒ₁₄、Ｒ₁₅、Ｒ₁₆、Ｒ₁₇、Ｒ₁₈、およびＲ₁₉の少なくとも１つは、エーテル結合を含み、他の実施形態において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀、Ｒ₁₁、Ｒ₁₂、Ｒ₁₃、Ｒ₁₄、Ｒ₁₅、Ｒ₁₆、Ｒ₁₇、Ｒ₁₈、およびＲ₁₉の少なくとも１つは、ケイ素原子または別のヘテロ原子を含む。Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀、Ｒ₁₁、Ｒ₁₂、Ｒ₁₃、Ｒ₁₄、Ｒ₁₅、Ｒ₁₆、Ｒ₁₇、Ｒ₁₈、およびＲ₁₉は、例えば、それぞれ独立に、水素化物基、ヒドロキシ基、アルキル基、アルケニル基、アルキニル基、アリール基、イミニル基、アルコキシ基、アルケノキシ基、アルキノキシ基、アリールオキシ基、カルボキシ基、アルキルカルボニルオキシ基、アルケニルカルボニルオキシ基、アルキニルカルボニルオキシ基、アリールカルボニルオキシ基、アルキルチオ基、アルケニルチオ基、アルキニルチオ基、アリールチオ基、シアノ基、Ｎ−置換アミノ基、アルキルカルボニルアミノ基、Ｎ−置換アルキルカルボニルアミノ基、アルケニルカルボニルアミノ基、Ｎ−置換アルケニルカルボニルアミノ基、アルキニルカルボニルアミノ基、Ｎ−置換アルキニルカルボニルアミノ基、アリールカルボニルアミノ基、およびＮ−置換アリールカルボニルアミノ基から選択することができる。式（３５）〜（３７）において、Ｒ₂₀は、いくつかの実施形態において、１〜２０個の炭素原子を含む２価の有機基であり、他の実施形態において、Ｒ₂₀は、２０個超の炭素原子を含む２価の有機基である。Ｒ₂₀は、例えば、アルキレン基、アルケニレン基、およびアルキニレン基から選択することができる。

The phosphorane represented by these is mentioned. In formulas (30)-(37), R ₁ , R ₂ , and R ₃ may correspond to X ₁ , X ₂ , and X ₃ according to formula (3). _{R 1, R 2, R 3} , R 4, R 5, R 6, R 7, R 8, R 9, R 10, R 11, R 12, R 13, R 14, R 15, R 16, R 17 , R ₁₈ , and R ₁₉ may be the same or different, and in some embodiments, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , and R ₁₉ are organic containing 1 to 20 carbon atoms It is a group. In other embodiments, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , and R ₁₉ are organic groups containing more than 20 carbon atoms. In some embodiments, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R _At least one of ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , and R ₁₉ includes an ether linkage, and in other embodiments, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , R ₁₅ , R ₁₆ , R ₁₇ , R ₁₈ , and R ₁₉ are at least a silicon atom or another hetero Contains atoms. _{R 1, R 2, R 3} , R 4, R 5, R 6, R 7, R 8, R 9, R 10, R 11, R 12, R 13, R 14, R 15, R 16, R 17 , R ₁₈ and R ₁₉ are each independently, for example, a hydride group, a hydroxy group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an iminyl group, an alkoxy group, an alkenoxy group, an alkynoxy group, an aryloxy group, Carboxy group, alkylcarbonyloxy group, alkenylcarbonyloxy group, alkynylcarbonyloxy group, arylcarbonyloxy group, alkylthio group, alkenylthio group, alkynylthio group, arylthio group, cyano group, N-substituted amino group, alkylcarbonylamino group N-substituted alkylcarbonylamino group, alkenylcarbonylamino group, N-substituted alkenylcarbonylamino group, · The alkenyl carbonylamino group, N- substituted alkynyl carbonyl amino group may be selected arylcarbonylamino group, and N- substituted arylcarbonylamino group. In formulas (35) to (37), R ₂₀ is a divalent organic group containing 1 to 20 carbon atoms in some embodiments, and in other embodiments, R ₂₀ is 20 It is a divalent organic group containing a super carbon atom. R ₂₀ can be selected from, for example, an alkylene group, an alkenylene group, and an alkynylene group.

[0159] When A is phosphorus, further examples of silicon-containing compounds according to formula (3) include:

で表されるホスフェートおよびホスフェート誘導体が挙げられる。
式（３８）〜（４１）において、Ｒ₁、Ｒ₂、およびＲ₃は、式（３）によるＸ₁、Ｘ₂、およびＸ₃に相当し得る。Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀、およびＲ₁₁は、同一であっても異なっていてもよく、いくつかの実施形態において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀、およびＲ₁₁の少なくとも１つは、１〜２０個の炭素原子を含む有機基である。他の実施形態において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀、およびＲ₁₁の少なくとも１つは、２０個超の炭素原子を含む有機基である。いくつかの実施形態において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀、およびＲ₁₁の少なくとも１つは、エーテル結合を含み、他の実施形態において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀、およびＲ₁₁の少なくとも１つは、ケイ素原子または別のヘテロ原子を含む。Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀、およびＲ₁₁は、例えば、それぞれ独立に、水素化物基、ヒドロキシ基、アルキル基、アルケニル基、アルキニル基、アリール基、イミニル基、アルコキシ基、アルケノキシ基、アルキノキシ基、アリールオキシ基、カルボキシ基、アルキルカルボニルオキシ基、アルケニルカルボニルオキシ基、アルキニルカルボニルオキシ基、アリールカルボニルオキシ基、アルキルチオ基、アルケニルチオ基、アルキニルチオ基、アリールチオ基、シアノ基、Ｎ−置換アミノ基、アルキルカルボニルアミノ基、Ｎ−置換アルキルカルボニルアミノ基、アルケニルカルボニルアミノ基、Ｎ−置換アルケニルカルボニルアミノ基、アルキニルカルボニルアミノ基、Ｎ−置換アルキニルカルボニルアミノ基、アリールカルボニルアミノ基、およびＮ−置換アリールカルボニルアミノ基から選択することができる。式（４１）において、Ｒ₁₂は、いくつかの実施形態において、１〜２０個の炭素原子を含む２価の有機基であり、他の実施形態において、Ｒ₁₂は、２０個超の炭素原子を含む２価の有機基である。Ｒ₁₂は、例えば、アルキレン基、アルケニレン基、およびアルキニレン基から選択することができる。

And phosphate derivatives represented by the formula:
In formulas (38) to (41), R ₁ , R ₂ , and R ₃ may correspond to X ₁ , X ₂ , and X ₃ according to formula (3). R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , and R ₁₁ may be the same or different, and some implementations In embodiments, at _{least one} of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , and R ₁₁ has 1 to 20 carbon atoms. Contains organic groups. In other embodiments, at _{least one} of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , and R ₁₁ is greater than 20 carbons. An organic group containing an atom. In some embodiments, at _{least one} of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , and R ₁₁ includes an ether linkage. In other embodiments, at _{least one} of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , and R ₁₁ is a silicon atom or another Of heteroatoms. R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , and R ₁₁ are each independently, for example, a hydride group, a hydroxy group, or an alkyl group. Alkenyl group, alkynyl group, aryl group, iminyl group, alkoxy group, alkenoxy group, alkynoxy group, aryloxy group, carboxy group, alkylcarbonyloxy group, alkenylcarbonyloxy group, alkynylcarbonyloxy group, arylcarbonyloxy group, alkylthio Group, alkenylthio group, alkynylthio group, arylthio group, cyano group, N-substituted amino group, alkylcarbonylamino group, N-substituted alkylcarbonylamino group, alkenylcarbonylamino group, N-substituted alkenylcarbonylamino group, alkynylcarbonyl Amino group, N-substituted alkynylcarbonyl It can be selected from a ruamino group, an arylcarbonylamino group, and an N-substituted arylcarbonylamino group. In formula (41), R ₁₂ is, in some embodiments, a divalent organic group containing 1-20 carbon atoms, and in other embodiments, R ₁₂ is greater than 20 carbon atoms. Is a divalent organic group. R ₁₂ can be selected from, for example, an alkylene group, an alkenylene group, and an alkynylene group.

[0160] Specific examples of phosphates according to formula (38) include:

で表されるトリス（トリメチルシリル）ホスフェートである。式（４２）において、メチル基の１つまたは複数は、構成要素の水素原子を別の化学元素または官能基で置換することなどにより修飾することができ、あるいは置換または無置換の形態の別のアルキル基、アルケニル基、アルキニル基、またはアリール基で置き換えることができると考えられる。式（４２）に記載されているホスフェートの他の官能化または修飾が考えられる。本発明の特定の実施形態による化合物（Ａは、リンである。）の他の例としては、これらに限定されないが、トリス（トリメチルシリル）ホスフェート、トリス（トリメチルシリル）ホスファイト、トリメチルシリルポリホスフェート、およびこれらの組合せが挙げられる。

It is tris (trimethylsilyl) phosphate represented by these. In formula (42), one or more of the methyl groups can be modified, such as by replacing a constituent hydrogen atom with another chemical element or functional group, or another in substituted or unsubstituted form. It is contemplated that an alkyl group, alkenyl group, alkynyl group, or aryl group can be substituted. Other functionalizations or modifications of the phosphate described in formula (42) are contemplated. Other examples of compounds according to certain embodiments of the invention (A is phosphorus) include, but are not limited to, tris (trimethylsilyl) phosphate, tris (trimethylsilyl) phosphite, trimethylsilylpolyphosphate, and these The combination of these is mentioned.

[0161] When A is sulfur, specific examples of silicon-containing compounds according to formula (3) include:

で表されるスルフィドが挙げられる。
式（４３）および（４４）において、Ｒ₁、Ｒ₂、およびＲ₃は、式（３）によるＸ₁、Ｘ₂、およびＸ₃に相当し得る。Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、およびＲ₇は、同一であっても異なっていてもよく、いくつかの実施形態において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、およびＲ₇の少なくとも１つは、１〜２０個の炭素原子を含む有機基である。他の実施形態において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、およびＲ₇の少なくとも１つは、２０個超の炭素原子を含む有機基である。いくつかの実施形態において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、およびＲ₇の少なくとも１つは、エーテル結合を含み、他の実施形態において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、およびＲ₇の少なくとも１つは、ケイ素原子または別のヘテロ原子を含む。Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、およびＲ₇は、例えば、それぞれ独立に、水素化物基、ヒドロキシ基、アルキル基、アルケニル基、アルキニル基、アリール基、イミニル基、アルコキシ基、アルケノキシ基、アルキノキシ基、アリールオキシ基、カルボキシ基、アルキルカルボニルオキシ基、アルケニルカルボニルオキシ基、アルキニルカルボニルオキシ基、アリールカルボニルオキシ基、アルキルチオ基、アルケニルチオ基、アルキニルチオ基、アリールチオ基、シアノ基、Ｎ−置換アミノ基、アルキルカルボニルアミノ基、Ｎ−置換アルキルカルボニルアミノ基、アルケニルカルボニルアミノ基、Ｎ−置換アルケニルカルボニルアミノ基、アルキニルカルボニルアミノ基、Ｎ−置換アルキニルカルボニルアミノ基、アリールカルボニルアミノ基、およびＮ−置換アリールカルボニルアミノ基から選択することができる。

The sulfide represented by these is mentioned.
In formulas (43) and (44), R ₁ , R ₂ , and R ₃ may correspond to X ₁ , X ₂ , and X ₃ according to formula (3). R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , and R ₇ may be the same or different, and in some embodiments, R ₁ , R ₂ , R ₃ , At least one of R ₄ , R ₅ , R ₆ , and R ₇ is an organic group containing 1 to 20 carbon atoms. In other embodiments, at least one of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , and R ₇ is an organic group containing more than 20 carbon atoms. In some embodiments, at least one of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , and R ₇ includes an ether linkage, and in other embodiments, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , and R ₇ contain a silicon atom or another heteroatom. R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , and R ₇ are each independently, for example, a hydride group, a hydroxy group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an iminyl group , Alkoxy group, alkenoxy group, alkynoxy group, aryloxy group, carboxy group, alkylcarbonyloxy group, alkenylcarbonyloxy group, alkynylcarbonyloxy group, arylcarbonyloxy group, alkylthio group, alkenylthio group, alkynylthio group, arylthio group Cyano group, N-substituted amino group, alkylcarbonylamino group, N-substituted alkylcarbonylamino group, alkenylcarbonylamino group, N-substituted alkenylcarbonylamino group, alkynylcarbonylamino group, N-substituted alkynylcarbonylamino group, arylcal It may be selected from Niruamino group, and N- substituted arylcarbonylamino group.

[0162] When A is sulfur, further examples of silicon-containing compounds according to formula (3) include:

で表されるものが挙げられる。式（４５）〜（５０）において、Ｒ₁、Ｒ₂、およびＲ₃は、式（３）によるＸ₁、Ｘ₂、およびＸ₃に相当し得る。Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀、Ｒ₁₁、Ｒ₁₂、Ｒ₁₃、Ｒ₁₄、およびＲ₁₅は、同一であっても異なっていてもよく、いくつかの実施形態において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀、Ｒ₁₁、Ｒ₁₂、Ｒ₁₃、Ｒ₁₄、およびＲ₁₅の少なくとも１つは、１〜２０個の炭素原子を含む有機基である。他の実施形態において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀、Ｒ₁₁、Ｒ₁₂、Ｒ₁₃、Ｒ₁₄、およびＲ₁₅の少なくとも１つは、２０個超の炭素原子を含む有機基である。いくつかの実施形態において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀、Ｒ₁₁、Ｒ₁₂、Ｒ₁₃、Ｒ₁₄、およびＲ₁₅の少なくとも１つは、エーテル結合を含み、他の実施形態において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀、Ｒ₁₁、Ｒ₁₂、Ｒ₁₃、Ｒ₁₄、およびＲ₁₅の少なくとも１つは、ケイ素原子または別のヘテロ原子を含む。Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、Ｒ₇、Ｒ₈、Ｒ₉、Ｒ₁₀、Ｒ₁₁、Ｒ₁₂、Ｒ₁₃、Ｒ₁₄、およびＲ₁₅は、例えば、それぞれ独立に、水素化物基、ヒドロキシ基、アルキル基、アルケニル基、アルキニル基、アリール基、イミニル基、アルコキシ基、アルケノキシ基、アルキノキシ基、アリールオキシ基、カルボキシ基、アルキルカルボニルオキシ基、アルケニルカルボニルオキシ基、アルキニルカルボニルオキシ基、アリールカルボニルオキシ基、アルキルチオ基、アルケニルチオ基、アルキニルチオ基、アリールチオ基、シアノ基、Ｎ−置換アミノ基、アルキルカルボニルアミノ基、Ｎ−置換アルキルカルボニルアミノ基、アルケニルカルボニルアミノ基、Ｎ−置換アルケニルカルボニルアミノ基、アルキニルカルボニルアミノ基、Ｎ−置換アルキニルカルボニルアミノ基、アリールカルボニルアミノ基、およびＮ−置換アリールカルボニルアミノ基から選択することができる。式（４９）および（５０）において、Ｒ₁₆は、いくつかの実施形態において、１〜２０個の炭素原子を含む２価の有機基であり、他の実施形態において、Ｒ₁₆は、２０個超の炭素原子を含む２価の有機基である。Ｒ₁₆は、例えば、アルキレン基、アルケニレン基、およびアルキニレン基から選択することができる。

The thing represented by is mentioned. In formulas (45)-(50), R ₁ , R ₂ , and R ₃ may correspond to X ₁ , X ₂ , and X ₃ according to formula (3). R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , and R ₁₅ are the same. In some embodiments, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ in some embodiments. , R ₁₃ , R ₁₄ , and R ₁₅ are organic groups containing 1 to 20 carbon atoms. In other embodiments, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , and R _At least one of ₁₅ is an organic group containing more than 20 carbon atoms. In some embodiments, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , and _At least one of R ₁₅ includes an ether bond, and in other embodiments R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R _At least one of ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , and R ₁₅ contains a silicon atom or another heteroatom. R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ , R ₁₄ , and R ₁₅ are, for example, Independently, hydride group, hydroxy group, alkyl group, alkenyl group, alkynyl group, aryl group, iminyl group, alkoxy group, alkenoxy group, alkynoxy group, aryloxy group, carboxy group, alkylcarbonyloxy group, alkenylcarbonyloxy group , Alkynylcarbonyloxy group, arylcarbonyloxy group, alkylthio group, alkenylthio group, alkynylthio group, arylthio group, cyano group, N-substituted amino group, alkylcarbonylamino group, N-substituted alkylcarbonylamino group, alkenylcarbonylamino Group, N-substituted alkenylcarbonylamino group, alkynylcarbonylamino group N- substituted alkynylcarbonyl amino group, can be selected arylcarbonylamino group, and N- substituted arylcarbonylamino group. In formulas (49) and (50), R ₁₆ is, in some embodiments, a divalent organic group containing 1-20 carbon atoms, and in other embodiments, R ₁₆ is 20 It is a divalent organic group containing a super carbon atom. R ₁₆ can be selected from, for example, an alkylene group, an alkenylene group, and an alkynylene group.

[0163] When A is sulfur, further examples of silicon-containing compounds according to formula (3) include:

で表されるスルホキシドが挙げられる。式（５１）および（５２）において、Ｒ₁、Ｒ₂、およびＲ₃は、式（３）によるＸ₁、Ｘ₂、およびＸ₃に相当し得る。Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、およびＲ₇は、同一であっても異なっていてもよく、いくつかの実施形態において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、およびＲ₇の少なくとも１つは、１〜２０個の炭素原子を含む有機基である。他の実施形態において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、およびＲ₇の少なくとも１つは、２０個超の炭素原子を含む有機基である。いくつかの実施形態において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、およびＲ₇の少なくとも１つは、エーテル結合を含み、他の実施形態において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、およびＲ₇の少なくとも１つは、ケイ素原子または別のヘテロ原子を含む。Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、およびＲ₇は、例えば、それぞれ独立に、水素化物基、ヒドロキシ基、アルキル基、アルケニル基、アルキニル基、アリール基、イミニル基、アルコキシ基、アルケノキシ基、アルキノキシ基、アリールオキシ基、カルボキシ基、アルキルカルボニルオキシ基、アルケニルカルボニルオキシ基、アルキニルカルボニルオキシ基、アリールカルボニルオキシ基、アルキルチオ基、アルケニルチオ基、アルキニルチオ基、アリールチオ基、シアノ基、Ｎ−置換アミノ基、アルキルカルボニルアミノ基、Ｎ−置換アルキルカルボニルアミノ基、アルケニルカルボニルアミノ基、Ｎ−置換アルケニルカルボニルアミノ基、アルキニルカルボニルアミノ基、Ｎ−置換アルキニルカルボニルアミノ基、アリールカルボニルアミノ基、およびＮ−置換アリールカルボニルアミノ基から選択することができる。

The sulfoxide represented by these is mentioned. In formulas (51) and (52), R ₁ , R ₂ , and R ₃ may correspond to X ₁ , X ₂ , and X ₃ according to formula (3). R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , and R ₇ may be the same or different, and in some embodiments, R ₁ , R ₂ , R ₃ , At least one of R ₄ , R ₅ , R ₆ , and R ₇ is an organic group containing 1 to 20 carbon atoms. In other embodiments, at least one of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , and R ₇ is an organic group containing more than 20 carbon atoms. In some embodiments, at least one of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , and R ₇ includes an ether linkage, and in other embodiments, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , and R ₇ contain a silicon atom or another heteroatom. R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , and R ₇ are each independently, for example, a hydride group, a hydroxy group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an iminyl group , Alkoxy group, alkenoxy group, alkynoxy group, aryloxy group, carboxy group, alkylcarbonyloxy group, alkenylcarbonyloxy group, alkynylcarbonyloxy group, arylcarbonyloxy group, alkylthio group, alkenylthio group, alkynylthio group, arylthio group Cyano group, N-substituted amino group, alkylcarbonylamino group, N-substituted alkylcarbonylamino group, alkenylcarbonylamino group, N-substituted alkenylcarbonylamino group, alkynylcarbonylamino group, N-substituted alkynylcarbonylamino group, arylcal It may be selected from Niruamino group, and N- substituted arylcarbonylamino group.

[0164] When A is sulfur, further examples of silicon-containing compounds according to formula (3) include:

で表されるスルホネートが挙げられる。式（５３）および（５４）において、Ｒ₁、Ｒ₂、およびＲ₃は、式（３）によるＸ₁、Ｘ₂、およびＸ₃に相当し得る。Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、およびＲ₇は、同一であっても異なっていてもよく、いくつかの実施形態において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、およびＲ₇の少なくとも１つは、１〜２０個の炭素原子を含む有機基である。他の実施形態において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、およびＲ₇の少なくとも１つは、２０個超の炭素原子を含む有機基である。いくつかの実施形態において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、およびＲ₇の少なくとも１つは、エーテル結合を含み、他の実施形態において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、およびＲ₇の少なくとも１つは、ケイ素原子または別のヘテロ原子を含む。Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、Ｒ₆、およびＲ₇は、例えば、それぞれ独立に、水素化物基、ヒドロキシ基、アルキル基、アルケニル基、アルキニル基、アリール基、イミニル基、アルコキシ基、アルケノキシ基、アルキノキシ基、アリールオキシ基、カルボキシ基、アルキルカルボニルオキシ基、アルケニルカルボニルオキシ基、アルキニルカルボニルオキシ基、アリールカルボニルオキシ基、アルキルチオ基、アルケニルチオ基、アルキニルチオ基、アリールチオ基、シアノ基、Ｎ−置換アミノ基、アルキルカルボニルアミノ基、Ｎ−置換アルキルカルボニルアミノ基、アルケニルカルボニルアミノ基、Ｎ−置換アルケニルカルボニルアミノ基、アルキニルカルボニルアミノ基、Ｎ−置換アルキニルカルボニルアミノ基、アリールカルボニルアミノ基、およびＮ−置換アリールカルボニルアミノ基から選択することができる。

The sulfonate represented by these is mentioned. In formulas (53) and (54), R ₁ , R ₂ , and R ₃ may correspond to X ₁ , X ₂ , and X ₃ according to formula (3). R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , and R ₇ may be the same or different, and in some embodiments, R ₁ , R ₂ , R ₃ , At least one of R ₄ , R ₅ , R ₆ , and R ₇ is an organic group containing 1 to 20 carbon atoms. In other embodiments, at least one of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , and R ₇ is an organic group containing more than 20 carbon atoms. In some embodiments, at least one of R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , and R ₇ includes an ether linkage, and in other embodiments, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , and R ₇ contain a silicon atom or another heteroatom. R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , and R ₇ are each independently, for example, a hydride group, a hydroxy group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an iminyl group , Alkoxy group, alkenoxy group, alkynoxy group, aryloxy group, carboxy group, alkylcarbonyloxy group, alkenylcarbonyloxy group, alkynylcarbonyloxy group, arylcarbonyloxy group, alkylthio group, alkenylthio group, alkynylthio group, arylthio group Cyano group, N-substituted amino group, alkylcarbonylamino group, N-substituted alkylcarbonylamino group, alkenylcarbonylamino group, N-substituted alkenylcarbonylamino group, alkynylcarbonylamino group, N-substituted alkynylcarbonylamino group, arylcal It may be selected from Niruamino group, and N- substituted arylcarbonylamino group.

[0165] Specific examples of sulfonates according to formula (54) include halo-substituted alkyl groups, specifically,

で表されるｔ−ブチルジメチルシリルトリフルオロメタンスルホネート、としてＲ₇が挙げられる。式（５５）において、アルキル基およびアルキルフルオライド基の１つまたは複数は、構成要素の水素またはフッ素原子を別の化学元素または官能基で置換することなどにより修飾することができ、あるいは置換または無置換の形態の別のアルキル基、アルケニル基、アルキニル基、またはアリール基で置き換えることができると考えられる。式（５５）に記載されているスルホネートの他の官能化または修飾が考えられる。

R ₇ may be mentioned as t-butyldimethylsilyl trifluoromethanesulfonate represented by: In formula (55), one or more of the alkyl and alkyl fluoride groups can be modified, such as by replacing the constituent hydrogen or fluorine atoms with another chemical element or functional group, or the like. It is envisioned that another alkyl group, alkenyl group, alkynyl group, or aryl group in unsubstituted form can be substituted. Other functionalizations or modifications of the sulfonate described in formula (55) are contemplated.

[0166] Further examples of suitable silicon-containing compounds include silicon-containing polymers such as

で表されるケイ素含有側基を有するポリホスフェートが挙げられる。式（５６）において、ｎは、少なくとも１または１超の負でない整数であり、ポリホスフェート中に含まれる繰り返し単位の数を表す。特定の実施形態について、ｎは、１〜１０、例えば、２〜１０の範囲であり、他の実施形態において、ｎは、少なくとも１０、例えば、少なくとも２０、少なくとも５０、少なくとも１００、少なくとも５００、または少なくとも１，０００であり、且つ、５，０００まで、１０，０００まで、５０，０００まで、１００，０００まで、またはこれを超える。Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、およびＲ₅は、同一であっても異なっていてもよく、いくつかの実施形態において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、およびＲ₅の少なくとも１つは、１〜２０個の炭素原子を含む有機基である。他の実施形態において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、およびＲ₅の少なくとも１つは、２０個超の炭素原子を含む有機基である。いくつかの実施形態において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、およびＲ₅の少なくとも１つは、エーテル結合を含み、他の実施形態において、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、およびＲ₅の少なくとも１つは、ケイ素原子または別のヘテロ原子を含む。Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、およびＲ₅は、例えば、それぞれ独立に、水素化物基、ヒドロキシ基、アルキル基、アルケニル基、アルキニル基、アリール基、イミニル基、アルコキシ基、アルケノキシ基、アルキノキシ基、アリールオキシ基、カルボキシ基、アルキルカルボニルオキシ基、アルケニルカルボニルオキシ基、アルキニルカルボニルオキシ基、アリールカルボニルオキシ基、アルキルチオ基、アルケニルチオ基、アルキニルチオ基、アリールチオ基、シアノ基、Ｎ−置換アミノ基、アルキルカルボニルアミノ基、Ｎ−置換アルキルカルボニルアミノ基、アルケニルカルボニルアミノ基、Ｎ−置換アルケニルカルボニルアミノ基、アルキニルカルボニルアミノ基、Ｎ−置換アルキニルカルボニルアミノ基、アリールカルボニルアミノ基、およびＮ−置換アリールカルボニルアミノ基から選択することができる。

The polyphosphate which has a silicon-containing side group represented by these is mentioned. In formula (56), n is a non-negative integer of at least 1 or more than 1, and represents the number of repeating units contained in the polyphosphate. For certain embodiments, n ranges from 1-10, such as 2-10, and in other embodiments, n is at least 10, such as at least 20, at least 50, at least 100, at least 500, or At least 1,000 and up to 5,000, up to 10,000, up to 50,000, up to 100,000, or more. R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ may be the same or different, and in some embodiments, R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ At least one of is an organic group containing 1 to 20 carbon atoms. In other embodiments, at least one of R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ is an organic group containing more than 20 carbon atoms. In some embodiments, at least one of R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ includes an ether linkage, and in other embodiments, R ₁ , R ₂ , R ₃ , R ₄ And at least one of R ₅ contains a silicon atom or another heteroatom. R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each independently, for example, a hydride group, a hydroxy group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an iminyl group, an alkoxy group, an alkenoxy group , Alkynoxy group, aryloxy group, carboxy group, alkylcarbonyloxy group, alkenylcarbonyloxy group, alkynylcarbonyloxy group, arylcarbonyloxy group, alkylthio group, alkenylthio group, alkynylthio group, arylthio group, cyano group, N- Substituted amino group, alkylcarbonylamino group, N-substituted alkylcarbonylamino group, alkenylcarbonylamino group, N-substituted alkenylcarbonylamino group, alkynylcarbonylamino group, N-substituted alkynylcarbonylamino group, arylcarbonylamino , And may be selected from N- substituted arylcarbonylamino group.

[0167] Furthermore, various compounds of formulas (3) to (56) may be formulated as salts with appropriate ions. Such compounds can contain any of the many substitutions described in Formulas (3)-(56) to interact with the counter ion. Examples of suitable silicon-containing salts include, but are not limited to, calcium metasilicate, tris [N, N-bis (trimethylsilyl) amido] erbium (III), sodium hexafluorosilicate, and combinations thereof. .

[0168] It is understood that certain compounds fall into multiple groups or groups as described in formulas (3)-(56) and related descriptions. Many compounds of embodiments of the present invention preferably contain one or more TMS structures. Such a TMS structure can promote proper decomposition of the additive and improve the performance of conventional electrolytes. Without being bound to a particular theory or mechanism of action, the presence of silicon in the additive facilitates the formation of silicon-containing films, layers, coatings, or regions on or in the electrode material be able to. Such film formation is described in more detail below.

[0169] Referring back to formulas (1) and (2), the amount of a particular compound can be expressed as a weight percent of the compound relative to the total weight (or weight percent) of the electrolyte. For example, the amount of the compound is about 0.01% to about 30% by weight, such as about 0.05% to about 30%, about 0.01% to about 20%, about 0.2%. % To about 15 wt%, about 0.2 wt% to about 10 wt%, about 0.2 wt% to about 5 wt%, or about 5 wt% to about 10 wt% When combined, the total amount of compound is about 0.01% to about 30% by weight, such as about 0.05% to about 30%, about 0.01% to about 20%, about 0%. It may range from 2% to about 15%, from about 0.2% to about 10%, from about 0.2% to about 5%, or from about 5% to about 10% by weight. The amount of compound can also be expressed as the ratio of the number of moles of compound per unit surface area of either or both electrode materials. For example, the amount of the compound is about 10 ⁻⁷ mol / m ² to about 10 ⁻² mol / m ² , for example, about 10 ⁻⁷ mol / m ² to about 10 ⁻⁵ mol / m ² , about 10 ⁻⁵ mol. / M ² to about 10 ⁻³ mol / m ² , about 10 ⁻⁶ mol / m ² to about 10 ⁻⁴ mol / m ² , or about 10 ⁻⁴ mol / m ² to about 10 ⁻² mol / m ² . Range may be sufficient. As described further below, the compounds can be consumed or can react, degrade, or undergo other modifications during initial battery cycling. Thus, the amount of compound can refer to the initial amount of compound used during the formation of the electrolyte according to formula (1) or (2), or prior to battery cycling (or any significant amount of battery It can refer to the initial amount of additive in the electrolyte solution (before cycling).

[0170] The performance characteristics of the resulting battery are the characteristics of the particular compound used to form the high voltage electrolyte according to formula (1) or (2), the amount of compound used, In the case of a combination of compounds, it can be determined by the relative amount of each compound in the combination. Thus, the performance characteristics thus obtained can be fine-tuned or optimized by appropriate selection of a set of compounds and adjusting the amount of compounds in formula (1) or (2). For example, for certain phosphates, such as tris (trimethylsilyl) phosphate, when used as an additive compound, the desired amount of compound is from about 0.5% to about 3%, such as from about 1% to about It may be in the range of 2% by weight. Fine adjustment of the amount of additive compound can be determined by factors such as the configuration of the battery and the properties of the positive or negative electrode material.

[0171] Formation according to formula (1) or (2) can be accomplished using various techniques, for example, mixing a base electrolyte and a set of additives and dispersing the set of additives in the base electrolyte. This can be done by dissolving a set of additives in the base electrolyte or otherwise bringing these components into contact with each other. The set of additives can be provided in liquid form, powder form (or another solid form), or a combination thereof. A set of additives can be incorporated into the electrolyte of formula (1) or (2) before, during, or after battery assembly.

[0172] The electrolytes described herein can be used for various batteries containing a high voltage positive electrode or a low voltage positive electrode, as well as in batteries operating at high temperatures. For example, the electrolyte can be used in place of or in conjunction with a conventional electrolyte for Li-ion batteries for operation at 4.2 V or higher.

[0173] FIG. 1 illustrates a Li-ion battery 100 implemented in accordance with one embodiment of the present invention. Battery 100 includes a negative electrode 102, a positive electrode 106, and a separator 108 disposed between negative electrode 102 and positive electrode 106. In the illustrated embodiment, the battery 100 also includes a high voltage electrolyte 104 that is disposed between the negative electrode 102 and the positive electrode 106 and is in a stable state during high voltage battery cycling.

[0174] The operation of battery 100 is based on reversible intercalation and deintercalation of Li ions into and from the anode 102 and cathode 106 host materials. Other implementations of the battery 100 are possible, such as those based on conversion chemistry. Referring to FIG. 1, the voltage of battery 100 is based on the redox potential of negative electrode 102 and positive electrode 106, and Li ions are occluded or released at a lower potential in the former and at a higher potential in the latter. In order to allow higher energy densities and higher voltage platforms to deliver that energy, the positive electrode 106 includes an active positive electrode material for high voltage operation above 4.2V. Suitable high voltage positive electrode materials are about 6V to about 4.5V, about 6V to about 5V, about 5.5V to about 4.5V relative to a lithium metal negative electrode (Li / Li ⁺ negative electrode) or other counter electrode. Or at a rate of about 5V to about 4.5V at a rate of 0.1C (or another reference rate higher or lower than 0.1C, eg, 0.05C, 0.5C, or 1C). And having a specific capacity of at least about 10 mAh / g, at least about 20 mAh / g, at least about 30 mAh / g, at least about 40 mAh / g, or at least about 50 mAh / g. Suitable high voltage positive electrode materials are about 6V to about 4.5V, about 6V to about 5V, about 5.5V to about 4.5V relative to a lithium metal negative electrode (Li / Li ⁺ negative electrode) or other counter electrode. Or about 5 V to about 4.5 V, substantially 15 mA / g (or another reference current higher or lower than 15 mA / g, eg, 7.5 mA / g, 75 mA / g, or 150 mA / g) Also included are those having a specific capacity of at least about 10 mAh / g, at least about 20 mAh / g, at least about 30 mAh / g, at least about 40 mAh / g, or at least about 50 mAh / g as measured by discharge at constant current. The values described for the specific capacity and current may be per unit mass of the positive electrode active material and can be expressed in units of mAh / (g of positive electrode active material) and mA / (g of positive electrode active material), respectively. Examples of suitable high voltage positive electrode materials include phosphate, fluorophosphate, fluorosulfate, fluorosilicate, spinel, Li-rich layered oxide, and composite layered oxide. Further examples of suitable positive electrode materials include spinel structure lithium metal oxide, layered structure lithium metal oxide, lithium-rich layered structure lithium metal oxide, lithium metal silicate, lithium metal phosphate, metal fluoride, metal oxide Products, sulfur, and metal sulfides. Examples of suitable negative electrode materials include conventional negative electrode materials used in Li-ion batteries, such as lithium, graphite (“Li _x C ₆ ”), and other carbon, silicate, or oxide-based negative electrode materials. It is done.

[0175] For example, one class of suitable high voltage phosphates can be expressed as Li _a (M1 _b M2 _c M3 _d M4 _e ) _f PO ₄ , where M1, M2, M3, and M4 are identical. M1 is Mn, Co, or Ni, and M2 is a transition metal such as Ti, V, Cr, Mn, Fe, Co, Ni, Zr, Nb, or Mo. , M3 is a transition metal or typical element optionally excluding elements of group VIA and VIIA, M4 is a transition metal or typical element optionally excluding elements of group VIA and VIIA, and 1.2 ≧ a ≧ 0.9 (or 1.2>a> 0.9), 1 ≧ b ≧ 0.6 (or 1>b> 0.6), 0.4 ≧ c ≧ 0 (or 0.4>c> 0), 0.2 ≧ d ≧ 0 (or 0.2>d> 0), 0.2 ≧ e ≧ 0 ( Others 0.2>e> 0), and a 1.2 ≧ f ≧ 0.9 (or 1.2>f> 0.9). Further details regarding this class of positive electrode materials can be found in Goodenough et al. "Challenges for Rechargeable Li Batteries," Chemistry of Materials 22, 587-603 (2010); Marom et al. , "A review of advanced and practical lithium battery materials," J. Mater. Chem. 21, 9938 (2011); Zhi-Ping et al. "Li-Site and Metal-Site Ion Doping in Phospho-Olive LiCoPO ₄ by First-Principles Calculation," Chin. Phys. Lett. 26 (3) 038202 (2009); and Fisher et al. "Lithium Battery Materials LiMPO ₄ (M) Mn, Fe, Co, and Ni): Insights into Defect Association, Transport Mechanisms, and Doping Behavior," Chem. Mater. 2008, 20, 5907-5915, the disclosures of which are incorporated herein by reference in their entirety.

[0176] For example, another class of suitable high voltage phosphates include lithium (Li), cobalt (Co), a first transition metal (M1), a second transition metal (M2) different from M1, and a phosphate. (PO ₄ ), and M1 and M2 are iron (Fe), titanium (Ti), vanadium (V), niobium (Nb), zirconium (Zr), hafnium (Hf), molybdenum (Mo, respectively). ), Tantalum (Ta), tungsten (W), manganese (Mn), copper (Cu), chromium (Cr), nickel (Ni), and zinc (Zn) (eg, as a dopant and / or its oxide) is selected, _{respectively, Li (1-x):} Co (1-yz): M1 y: M2 z: (PO 4) (1-a) ( wherein, -0.3 ≦ x ≦ 0.3; 0 .01 ≦ y ≦ 0.5; 0.01 ≦ z ≦ 0. -0.5 ≦ a ≦ 0.5; and 0.2 ≦ 1-yz ≦ 0.98) (as a simple notation), (1-x): ( 1-y-z): y : z: Li is defined by (1-a): Co: M1: M2: can have a molar ratio of PO _4. Preferably, M1 and M2 are each selected from iron (Fe), titanium (Ti), vanadium (V) and niobium (Nb) (eg, as a dopant and / or its oxide). Preferably, M1 is iron (Fe) (eg, as a dopant and / or oxide thereof) and M2 is titanium (Ti), vanadium (V), and niobium (Nb) (eg, dopant and / or As its oxide). Preferably, −0.3 ≦ x <0, −0.2 ≦ x <0, or −0.1 ≦ x <0. Preferably, M2 is Ti, and 0.05 ≦ z ≦ 0.25 or 0.05 ≦ z ≦ 0.2. Preferably, M2 is V, and 0.03 ≦ z ≦ 0.25 or 0.05 ≦ z ≦ 0.2. Preferably, 0.3 ≦ 1-yz ≦ 0.98, 0.5 ≦ 1-yz ≦ 0.98, or 0.7 ≦ 1-yz ≦ 0.98. Further details regarding this class of olivine cathode materials are entitled “Lithium Ion Battery Materials with Improved Properties”, filed Dec. 23, 2010, co-pending and co-owned US Provisional Application No. 61. No. 426,733, the entire disclosure of which is incorporated herein by reference.

[0177] For example, one class of suitable high voltage fluorophosphates can be expressed as Li _a (M1 _b M2 _c M3 _d M4 _e ) _f PO ₄ F _g , where M1, M2, M3, and M4 are M1 is Mn, Co, or Ni, and M2 is a transition metal such as Ti, V, Cr, Mn, Fe, Co, Ni, Zr, Nb, or Mo, M3 is a transition metal or typical element optionally excluding elements of group VIA and VIIA, M4 is a transition metal or typical element optionally excluding elements of group VIA and VIIA, 1.2 ≧ a ≧ 0.9 (or 1.2>a> 0.9), 1 ≧ b ≧ 0.6 (or 1>b> 0.6), 0.4 ≧ c ≧ 0 (or 0 .4>c> 0), 0.2 ≧ d ≧ 0 (or 0.2>d> 0), 0 2 ≧ e ≧ 0 (or 0.2>e> 0), 1.2 ≧ f ≧ 0.9 (or 1.2>f> 0.9), and 1.2 ≧ g ≧ 0 (or 1. 2>g> 0).

[0178] For example, one class of suitable high voltage fluorosilicates can be expressed as Li _a (M1 _b M2 _c M3 _d M4 _e ) _f SiO ₄ F, where M1, M2, M3, and M4 are identical. M1 is Mn, Co, or Ni and M2 is a transition metal such as Ti, V, Cr, Mn, Fe, Co, Ni, Zr, Nb, or Mo. M3 is a transition metal or typical element arbitrarily excluding elements of group VIA and VIIA, M4 is a transition metal or typical element optionally excluding elements of group VIA and VIIA, .2 ≧ a ≧ 0.9 (or 1.2>a> 0.9), 1 ≧ b ≧ 0.6 (or 1>b> 0.6), 0.4 ≧ c ≧ 0 (or 0. 4>c> 0), 0.2 ≧ d ≧ 0 (or 0.2>d> 0), 0. 2 ≧ e ≧ 0 (or 0.2>e> 0) and 1.2 ≧ f ≧ 0.9 (or 1.2>f> 0.9).

[0179] For example, another class of suitable high voltage fluorosilicates can be expressed as Li _a (M1 _b M2 _c M3 _d M4 _e ) _f SiO ₄ F _g , where M1, M2, M3, and M4 are M1 is Mn, Co, or Ni, and M2 is a transition metal such as Ti, V, Cr, Mn, Fe, Co, Ni, Zr, Nb, or Mo, M3 is a transition metal or typical element optionally excluding elements of group VIA and VIIA, M4 is a transition metal or typical element optionally excluding elements of group VIA and VIIA, 1.2 ≧ a ≧ 0.9 (or 1.2>a> 0.9), 1 ≧ b ≧ 0.6 (or 1>b> 0.6), 0.4 ≧ c ≧ 0 (or 0 .4>c> 0), 0.2 ≧ d ≧ 0 (or 0.2>d> 0), 0. ≧ e ≧ 0 (or 0.2>e> 0), 1.2 ≧ f ≧ 0.9 (or 1.2>f> 0.9), and 1.2 ≧ g ≧ 0 (or 1.2 >G> 0).

[0180] For example, one class of suitable high voltage spinels can be represented as Li _a (M1 _b M2 _c M3 _d M4 _e ) _f O ₄ , where M1, M2, M3, and M4 are identical. M1 is Mn or Fe, M2 is Mn, Ni, Fe, Co or Cu, and M3 is a transition metal such as Ti, V, Cr, Mn, Fe, Co, Ni, Zr, Nb, or Mo, and M4 is a transition metal or a typical element in which VIA and VIIA elements are arbitrarily excluded, and 1.2 ≧ a ≧ 0.9 (or 1.2 >A> 0.9) 1.7 ≧ b ≧ 1.2 (or 1.7>b> 1.2), 0.8 ≧ c ≧ 0.3 (or 0.8>c> 0.3) ), 0.1 ≧ d ≧ 0 (or 0.1>d> 0), 0.1 ≧ e ≧ 0 (or 0.1>e> 0), and 2 It is a 2 ≧ f ≧ 1.5 (or 2.2>f> 1.5). LMNO type positive electrode materials such as Li _1.05 Mn _1.5 Ni _0.5 O ₄ and LMO type materials such as LiMn ₂ O ₄ are included in this class. Further details regarding this class of positive electrode materials can be found in Goodenough et al. "Challenges for Rechargeable Li Batteries," Chemistry of Materials 22, 587-603 (2010); Marom et al. , "A review of advanced and practical lithium battery materials," J. Mater. Chem. , 21, 9938 (2011); and Yi et al. , “Recent developments in the doping of LiNi _0.5 Mn _1.5 O ₄ cathode material for 5V lithium-ion batteries,” Ionics (2011) 17: 383-389, the entire contents of which are incorporated herein by reference. Can be found).

[0181] For example, one class of suitable high voltage Li-rich layered oxides can be expressed as Li (Li _a M1 _b M2 _c M3 _d M4 _e ) _f O ₂ , where M1, M2, M3, and M4 may be the same or different, M1 is a transition metal, eg, Mn, Fe, V, Co, or Ni, and M2 is a transition metal, eg, Mn, Fe, V, Co Or M3 is a transition metal, for example, Mn, Fe, V, Co, or Ni, and M4 is a transition metal or a typical element optionally excluding elements of Group VIA and VIIA, 0.4 ≧ a ≧ 0.05 (or 0.4>a> 0.05), 0.7 ≧ b ≧ 0.1 (or 0.7>b> 0.1), 0.7 ≧ c ≧ 0.1 (or 0.7>c> 0.1), 0.7 ≧ d ≧ 0.1 (or 0.7>d> 0.1) , 0.2 ≧ e ≧ 0 (or 0.2>e> 0), and a 1.2 ≧ f ≧ 0.9 (or 1.2>f> 0.9). OLO-type positive electrode materials are included in this classification. Further details regarding this class of positive electrode materials can be found in Goodenough et al. "Challenges for Rechargeable Li Batteries," Chemistry of Materials 22, 587-603 (2010); Marom et al. "A review of advanced and practical lithium battery materials" J. Mater. Chem. 21, 9938 (2011); Johnson et al. , “Synthesis, Characterization and Electrochemistry of Lithium Battery Electrodes: xLi ₂ MnO ₃ (1-x) LiMn _0.333 Ni _0.333 Co _0.333 O ₂ (0 <x <0.7),” Chem. Mater. , 20, 6095-6106 (2008); and Kang et al. , “Interpreting the structural and electrical chemical of 0.5Li ₂ MnO ₃ .0.5LiMO ₂ electrodes for lithium batteries (M = Mn _0.5-x Ni _0.5-x Co _2x , 0 = x 0.5) Mater. Chem. , 17, 2069-2077 (2007), the entire disclosures of which are incorporated herein by reference.

[0182] For example, a suitable high voltage, one class of complex layered oxide can be represented as _{(Li 2 M1 a M2 b O} 3) c (LiM3 d M4 e M5 f O 2) g, M1, M2, M3, M4, and M5 may be the same or different, M1 is a transition metal, eg, Mn, Fe, V, Co, or Ni, and M2 is a transition metal, eg, Mn, Fe, V, Co, or Ni, M3 is a transition metal, eg, Mn, Fe, V, Co, or Ni, and M4 is a transition metal, eg, Mn, Fe, V, Co, Or Ni, and M5 is a transition metal or a typical element in which elements of Group VIA and VIIA are arbitrarily excluded, and 1.1 ≧ a ≧ 0 (or 1.1>a> 0), 0.5 ≧ b ≧ 0 (or 0.5>b> 0), 0.7 ≧ c ≧ 0 (or 0. >C> 0), 1 ≧ d ≧ 0 (or 1>d> 0), 1 ≧ e ≧ 0 (or 1>e> 0), 1 ≧ f ≧ 0 (or 1>f> 0), and 1 ≧ g ≧ 0.5 (or 1>g> 0.5). Further details regarding this class of positive electrode materials can be found in Goodenough et al. , "" Challenges for Rechargeable Li Batteries, "" Chemistry of Materials 22, 587-603 (2010); Marom et al. "" A review of advanced and practical lithium battery materials "" J. Mater. Chem. 21, 9938 (2011); Johnson et al. , "" Synthesis, Characterization and Electrochemistry of Lithium Battery Electrodes: xLi 2 MnO 3 (1-x) LiMn 0.333 Ni 0.333 Co 0.333 O 2 (0 <x <0.7), "" Chem. Mater. , 20, 6095-6106 (2008); and Kang et al. , “” Interpreting the structural and electrical chemical of 0.5Li ₂ MnO ₃ .0.5LiMO ₂ electrodes for lithium batteries (M = Mn _0.5-x Ni _0.5-x Co _2x , 0 = ” J. et al. Mater. Chem. , 17, 2069-2077 (2007), the disclosures of which are incorporated herein by reference in their entirety.

[0183] Turning now to FIG. 2, this illustrates the operation of a Li-ion battery and a non-limiting exemplary mechanism of action of an improved electrolyte according to one embodiment of the present invention. While not being bound by any particular theory that is not set forth in the claims, including a set of one or more stabilizing additive compounds in an electrolyte (eg, during its conditioning) The battery operation can inactivate the high voltage positive electrode material, thereby reducing or preventing reactions between the bulk electrolyte component and the positive electrode material that can degrade the performance of the battery.

[0184] Referring to FIG. 2, electrolyte 202 includes a base electrolyte, and during initial battery cycling, components in the base electrolyte are on or adjacent to negative electrode 204 (solid electrolyte interface (“SEI”)). ) In situ formation of a protective coating (in the form of 206). The negative electrode SEI 206 can inhibit the reductive decomposition of the high voltage electrolyte 202. Preferably, and without being bound by theory not described in the claims, for operation at voltages above 4.2 V, the electrolyte 202 is on or adjacent to the positive electrode 200 (SEI 208 or It may also include a set of additives that can assist in situ formation of the protective coating (in the form of another derivative). The positive electrode SEI 208 can inhibit oxidative decomposition of the high voltage electrolyte 202 that may otherwise occur during high voltage operation. Therefore, the positive electrode SEI 208 can inhibit the oxidation reaction in a manner corresponding to the inhibition of the reduction reaction by the negative electrode SEI 206. In the illustrated embodiment, the positive electrode SEI 208 can have a thickness in the submicron range and is present in a set of one or more additives, eg, a set of one or more additions. A set of one or more chemical elements corresponding to or derived from silicon or other heteroatoms contained in the agent may be included. Advantageously, the set of one or more additives can preferentially deactivate the positive electrode 200 and selectively contribute to film formation on the positive electrode 200 rather than the negative electrode 204. Can do. Such preferential or selective film formation on the positive electrode 200 (along with the negative electrode SEI 206) is done with little further film formation on the negative electrode 204 that otherwise degrades the performance of the battery due to loss of resistance. Stability to oxidative degradation can be imparted without or at all. More generally, the set of one or more additives can degrade below the redox potential of the positive electrode material and above the redox potential of SEI formation on the negative electrode 204.

[0185] While not being bound by any particular theory not set forth in the claims, the formation of positive electrode SEI 208 may occur by one or more of the following mechanisms.
(1) A set of additive compounds can decompose to form positive electrode SEI 208, which inhibits further oxidative degradation of the electrolyte components.
(2) A set of additive compounds can form a complex with an intermediate product, such as LiPF ₆ or a positive electrode material, which is subsequently decomposed to form positive electrode SEI 208, which Inhibits further oxidative degradation of the electrolyte components.
(3) A set of additive compounds can form a complex with an intermediate product, such as LiPF ₆ , which then decomposes during the initial charge. The decomposition products thus obtained can then be further decomposed during initial charging to form positive electrode SEI 208, which inhibits further oxidative decomposition of the electrolyte components.
(4) A set of additive compounds can stabilize the positive electrode material by preventing dissolution of metal ions.

[0186] According to one embodiment of the invention, other mechanisms of action of the electrolyte 202 are contemplated. For example, instead of (or in combination with) forming positive electrode SEI 208 or improving its quality, a set of one or more additives or derivatives thereof (eg, degradation products thereof) can be converted into negative electrode SEI 206. The negative electrode SEI 206 can be formed or its quality can be improved, for example, to reduce the resistance to Li ion diffusion due to. As another example, a set of one or more additives or derivatives thereof (eg, degradation products thereof) may react chemically with other electrolyte components or form a complex, The stability of the electrolytic solution 202 can be improved. As a further example, a set of one or more additives or derivatives thereof (e.g., degradation products thereof) may react with other electrolyte components or dissolved electrodes in electrolyte 202 by chemical reaction or complex formation. The decomposition products of the material can be removed. Any one or more of positive electrode SEI 208, negative electrode SEI 206, and other degradation products or composites can be viewed as a derivative, which is present in a set of one or more additives, For example, it may contain a set of one or more chemical elements corresponding to or derived from silicon or other heteroatoms contained in a set of additives.

[0187] The electrolytes described herein can be conditioned prior to use in commercial or commercial applications. For example, a battery containing an electrolyte can be conditioned by cycling prior to sale or commercial use. The method of conditioning a battery can include, for example, conditioning the battery for sale. Such methods include, for example, preparing a battery and cycling such a battery for at least 1 cycle, at least 2 cycles, at least 3 cycles, at least 4 cycles, or at least 5 cycles. Each cycle can include 0.05 C (eg, 7.5 mA / g current) at 4.95 V to 2.0 V (or another voltage range) relative to a reference counter electrode, eg, a graphite negative electrode. Charging the battery at a rate of, and discharging the battery. Charging and discharging can be done at higher or lower rates, for example, at a rate of 0.1 C (eg, 15 mA / g current), at a rate of 0.5 C (eg, 75 mA / g current), or 1 C ( For example, it can be performed at a current of 150 mA / g).

[0188] The electrochemical stability of the electrolyte in the battery cell can be evaluated by measuring the residual current, or the current passing through the cell after the battery is fully charged or discharged. Residual current can be measured by fully charging the cell and then applying a voltage beyond the equilibrium potential. When the cell is fully charged, the residual current reflects the degree of electrochemical decomposition of the material in the cell. A low residual current compared to the control indicates enhanced electrochemical stability. Without being bound by a particular theory or mechanism of action, when the equilibrium potential of the cell is exceeded, electrochemical decomposition of the electrolyte causes electron transfer from the anode to the electrolyte and from the electrolyte to the cathode. At least in part, current can flow through the battery cell. Additive compounds according to embodiments of the present invention improve electrolyte performance by any of the mechanisms proposed herein under conditions that can typically result in electrolyte degradation. Such an improvement in electrochemical stability helps to solve problems existing in known electrolytes.

[0189] As will be appreciated from the many examples below, the additive compounds of certain embodiments of the present invention improve the performance of conventional electrolytes in high voltage cells, both at room temperature and at elevated temperatures. In addition, the compounds of certain embodiments of the present invention improve the performance of conventional electrolytes in high voltage, low voltage cells.

[0190] Electrolytes containing certain OMTS additives showed an improvement in residual current compared to conventional electrolytes in standard CR2032 (Hohsen) coin cells. The cell was held at 50 ° C. for 10 hours at 4.5V, 4.9V and 5.1V, and the residual current was observed. Lower residual current for electrolytes containing certain OMTS additives indicates reduced electrolyte decomposition.

[0191] The OTMS additive according to certain embodiments improves coulomb efficiency over the reference electrolyte in high voltage cells. Certain OTMS additives showed about a 6% improvement in Coulomb efficiency compared to the control electrolyte.

[0192] Certain OTMS additives showed as much as about 19% improvement in room temperature cycle life of the high voltage spinel (LMNO type) cathode material compared to the control electrolyte.

[0193] The NTMS additive according to certain embodiments improves room temperature cycle life over a reference electrolyte in a high voltage cell. Certain NTMS additives showed as much as about 11% improvement in room temperature cycle life of the high voltage spinel (LMNO type) cathode material compared to the control electrolyte.

[0194] Certain TMS additives according to certain embodiments improve cycle life and Coulomb efficiency at higher additive concentrations than those used for certain OTMS and NTMS additives. Certain TMS additives showed about a 3% improvement in Coulomb efficiency compared to the control electrolyte. Certain TMS additives showed as much as about 10% improvement in room temperature cycle life of the high voltage spinel (LMNO type) cathode material compared to the control electrolyte.

[0195] Certain OTMS additives showed as much as about 110% improvement in the high temperature spin life of the high voltage spinel (LMNO type) cathode material compared to the control electrolyte. Certain OTMS additives showed as much as about 200% improvement in the high temperature cycle life of the LMO type cathode material compared to the control electrolyte. Certain OTMS additives improve the efficiency of the first cycle and the reversible capacity of the first cycle in the high voltage spinel (LMNO type) cathode material compared to the control electrolyte.

[0196] Certain OTMS additives showed as much as about 70% improvement in the high temperature cycle life of the NMC type cathode material compared to the control electrolyte. The OTMS additive according to certain embodiments improved room temperature cycle life over the reference electrolyte in the NMC type cathode material.

[0197] Certain OTMS additives showed as much as about 70% improvement in room temperature cycle life of the lithiated layered oxide (OLO type) cathode material compared to the control electrolyte. Certain OTMS additives showed as much as about 130% improvement in the high temperature cycle life of the high voltage OLO type cathode material compared to the control electrolyte. Certain OTMS additives showed as much as about 2.5% improvement in room temperature energy efficiency of high voltage OLO type cathode materials compared to the control electrolyte.

[0198] Certain OTMS additives showed an improvement of about 18% in the coulombic efficiency of the high voltage olivine cathode material (CM1 type) compared to the control electrolyte. Certain OTMS additives showed as much as about 400% improvement in room temperature cycle life of the high voltage CM1 type cathode material compared to the control electrolyte.

[0199] The NTMS additive according to certain embodiments improves room temperature cycle life over a reference electrolyte in a high voltage cell. Certain NTMS additives showed as much as about 410% improvement in room temperature cycle life of the high voltage CM1 type cathode material compared to the control electrolyte.

[0200] The following examples describe certain aspects of some embodiments of the present invention, and illustrate and provide descriptions for those skilled in the art. The examples should not be construed as limiting the invention, as the examples only provide specific methods useful in understanding and practicing some embodiments of the invention.

Example 1
Method for the formation and characterization of battery cells containing stabilizers
[0201] Battery cells were formed in a glove box filled with high purity argon (M-Braun, O ₂ and moisture content <0.1 ppm). First, poly (vinylidene fluoride) (Sigma Aldrich), carbon black (Super P Li, TIMCAL), and doped LiCoPO ₄ cathode material (Li _(1-x) : Co _(1-yz) : Fe _y : Ti _z : (PO ₄ ) _(1-a) ) is mixed in 1-methyl-2-pyrrolidinone (Sigma Aldrich) and the resulting slurry is deposited on an aluminum current collector and dried. To form a positive electrode material composition film. Lithium or graphite negative electrode was used. In the case of a graphite negative electrode, graphitic carbon (mesocarbon microbeads or MCMB) is used as a solvent using 1-methyl-2-pyrrolidinone (Sigma Aldrich) as a solvent, and poly (vinylidene fluoride) (Sigma Aldrich), carbon black ( Super P Li, TIMCAL) and the slurry thus obtained was deposited on a copper current collector and dried to form a negative electrode material composition film. In a coin cell type assembly (CR2025, Hohsen), each battery cell including a positive electrode composition coating, Millipore glass fiber or polypropylene separator, and a lithium or graphite negative electrode was assembled. A conventional electrolyte was mixed with the stabilizing additive compound and added to the battery cell. The battery cells were sealed and cycled between a specific voltage range (eg, about 2V to about 4.95V) at a specific temperature (eg, room temperature or 25 ° C.).

(Example 2)
Characterization of battery cells containing stabilizers
[0202] Test using the method of Example 1 with about 10% by weight of tris (trimethylsilyl) phosphate dispersed in a conventional electrolyte (ethylene carbonate, dimethyl carbonate, and 1M LiPF ₆ ) as a stabilizer. For battery cells (labeled “ttsp”) and for control battery cells (labeled “EC / DMC, 1M LiPF ₆ ”) containing a conventional electrolyte but no stabilizer. The performance characteristics were measured. Each of the test cells and control cells, doped LiCoPO ₄ cathode material _{(Li (1-x):} Co (1-yz): Fe y: Ti z: (PO 4) (1-a)) and It was included. FIG. 3A (top) shows capacity retention rates with and without stabilizers over several cycles, expressed as a percentage of the initial specific capacity during discharge maintained in a particular cycle. It is a comparison. As can be appreciated from this figure, the inclusion of a stabilizer improves cycle life, and after about 26 cycles, the initial discharge capacity is about 78% (less than about 50% without the stabilizer). Maintained). FIG. 3B (bottom) compares the coulombic efficiency with and without the stabilizer over several cycles, and the inset shows the measurement of coulomb efficiency with the stabilizer. It is an enlarged view. As can be appreciated from this figure, the inclusion of a stabilizer improved coulomb efficiency and increased from an initial value of about 95% to reach a stable or steady value of about 97% (stabilizer). Compared to a value in the range of about 10% to about 45% without the use of).

(Example 3)
Characterization of battery cells containing stabilizers
[0203] Using the method of Example 1, tris (trimethylsilyl) phosphate (denoted "ttsp") dispersed in a conventional electrolyte (ethylene carbonate, ethyl methyl carbonate, and 1M LiPF ₆ ). Performance characteristics are shown for test battery cells containing as a stabilizer and for control battery cells (labeled “EC: EMC, 1M LiPF ₆ ”) containing a conventional electrolyte but no stabilizer. It was measured. Each of the test cells and control cells, doped LiCoPO ₄ cathode material _{(Li (1-x):} Co (1-yz): Fe y: Ti z: (PO 4) (1-a)) and And cycling from about 2 V to about 4.95 V at a current of about 150 mA / g and room temperature (25 ° C.). Figure 4 compares capacity retention rates with and without stabilizers over several cycles expressed as a percentage of the initial specific capacity at the time of discharge maintained in a particular cycle. It is. As can be appreciated from this figure, the inclusion of a stabilizer improves cycle life and after about 100 cycles the initial discharge capacity is about 80% (compared to about 20% without the stabilizer). And about 68% of the initial discharge capacity after 200 cycles (compared to less than about 20% without the stabilizer). Inclusion of the stabilizer also improved the coulomb efficiency and maintained a value above about 98% after 100 cycles.

[0204] To evaluate the stability at high temperature, cycling was performed at 50 ° C. FIG. 5 superimposes the results of the capacity retention rate measurement at 50 ° C. on FIG. As can be appreciated from this figure, desirable cycle life characteristics are maintained even at temperatures as high as 50 ° C.

Example 4
Characterization of battery cells containing stabilizers
[0205] Using the method of Example 1, for tris (trimethylsilyl) phosphate as a stabilizer dispersed in a conventional electrolyte (ethylene carbonate: ethyl methyl carbonate (1: 2) and 1M LiPF ₆ ), Performance characteristics were measured. Each test cell is doped LiCoPO ₄ cathode material _{(Li (1-x):} Co (1-yz): Fe y: Ti z: (PO 4) (1-a)) and those containing graphite anode Met. Measurements were taken at different concentrations of stabilizer, ie, about 0.25%, about 0.5%, about 1%, about 2%, about 10%, and about 15%.

[0206] Fig. 6 is a plot of capacity retention as a function of stabilizer concentration (expressed as a percentage of specific capacity during discharge in the fifth cycle, maintained after 50 cycles). As can be appreciated from this figure, capacity retention varies with stabilizer concentration, ranging from about 60% for low concentration stabilizers to about 45% for high concentration stabilizers. At about 90% for intermediate concentrations of stabilizer.

FIG. 7 is a plot of Coulomb efficiency at the 50th cycle according to the concentration of the stabilizer. As can be appreciated from this figure, the coulomb efficiency also varies with the concentration of the stabilizer, increasing from about 87% for the low level stabilizer to about 98% for the intermediate level stabilizer. However, it shows a slight decrease for higher concentrations of stabilizer.

(Example 5)
Characterization of battery cells containing stabilizers
[0208] Using the method of Example 1, 2 wt% tris (trimethylsilyl) as a stabilizer dispersed in a conventional electrolyte (ethylene carbonate: ethyl methyl carbonate (1: 2) and 1M LiPF ₆ ). Cyclic voltammetry measurements were performed on phosphate. The measurement was performed on the battery cell including the LiMn ₂ O ₄ positive electrode and the Li negative electrode. FIG. 8 shows the superimposed cyclic voltammograms for the first to third cycles, and FIG. 9 shows the superimposed cyclic voltammograms for the fourth to sixth cycles. As can be appreciated from these figures, a large resistance increase is first observed during the charging process of the first cycle and is indicated during the subsequent cycle (shown as “Reduction in resistance” in FIG. 8). This resistance is reduced (as indicated by the arrows that appear). Also, during the discharge phase of the first cycle, a peak at about 3.6 V is first observed, and during the subsequent cycle (dotted elliptical area displayed as “disappearance of peak” in FIG. 8). This peak gradually disappears (as indicated by). While not being bound to a particular theory not stated in the claims, this transition behavior observed in the cyclic voltammogram is either directly (or directly or Indirectly may indicate the formation of intermediate products that may be involved (eg, derivatives of electrolyte additives).

(Example 6)
Characterization of battery cells containing stabilizers
[0209] For a test battery cell comprising tris (trimethylsilyl) phosphate (labeled "ttsp") dispersed in a conventional electrolyte (ethylene carbonate, ethyl methyl carbonate, and 1M LiPF ₆ ) as a stabilizer, And the performance characteristics were measured for a control battery cell (labeled “EC: EMC (1: 2), 1M LiPF ₆ )) containing a conventional electrolyte but no stabilizer. Each of the test cells and control cells, doped LiCoPO ₄ cathode material _{(Li (1-x):} Co (1-yz): Fe y: Ti z: (PO 4) (1-a)) and And held at about 50 ° C. for 8 days in a fully charged state and cycled from about 2 V to about 4.95 V at a rate of about 1 C (150 mA / g) and room temperature (25 ° C.). FIG. 10 compares capacity retention rates with and without stabilizers over several cycles, expressed as a percentage of the initial specific capacity during discharge maintained in a particular cycle. It is. As can be appreciated from this figure, inclusion of a stabilizer improved cycle life following aging.

(Example 7)
Characterization of battery cells containing stabilizers
[0210] The effectiveness of tris (trimethylsilyl) phosphate as a stabilizer was tested on other cathode materials. In one set of tests, a test battery comprising tris (trimethylsilyl) phosphate (labeled “ttsp”) dispersed in a conventional electrolyte (ethylene carbonate, ethyl methyl carbonate, and 1M LiPF ₆ ) as a stabilizer. The performance characteristics were measured for the cell and for a control battery cell (labeled “EC: EMC (1: 2), 1M LiPF ₆ )) containing a conventional electrolyte but no stabilizer. . Each of the test and control battery cells contained LiMn _1.5 Ni _0.5 O ₄ cathode material and were cycled from about 3V to about 4.9V at a rate of about 1C and about 50 ° C. after formation at room temperature. FIG. 11 compares capacity retention rates with and without stabilizers over several cycles, expressed as a percentage of the initial specific capacity during discharge maintained in a particular cycle. It is. As can be appreciated from this figure, the inclusion of the stabilizer improved the cycle life for the LiMn _1.5 Ni _0.5 O ₄ cathode material.

[0211] In another set of tests, tris (trimethylsilyl) phosphate (labeled "ttsp") dispersed in a conventional electrolyte (ethylene carbonate, ethyl methyl carbonate, and 1M LiPF ₆ ) is used as a stabilizer. As well as for the control battery cells (labeled “EC: EMC (1: 2), 1M LiPF ₆ ) with conventional electrolytes but no stabilizers, as well as performance characteristics. Was measured. Each of the test battery cell and the control battery cell contains LiMn ₂ O ₄ cathode material (about 4.2V) and, after formation at room temperature, at a rate of about 1C and about 3V to about 4.5V at about 50 ° C. Cycling. FIG. 12 compares the capacity retention rates with and without the stabilizer over several cycles, expressed as a percentage of the initial discharge capacity maintained in a particular cycle. As can be appreciated from this figure, the inclusion of the stabilizer also improved the cycle life for the LiMn ₂ O ₄ cathode material. Including the stabilizer also shows FIG. 13 (shows open circuit voltage measurement at about 50 ° C. after formation at room temperature) and FIG. 14 (constant voltage of about 5.1 V and residual current at about 50 ° C. shows the measurement.) as can be voted, it resulted in reduced and low residual current self-discharge for LiMn ₂ O ₄ cathode material.

(Example 8)
Characterization of battery cells containing stabilizers
[0212] Performance characteristics were measured for various stabilizers dispersed in conventional electrolytes (ethylene carbonate, dimethyl carbonate, and 1M LiPF ₆ ). Each test battery cells and each control cell is doped LiCoPO ₄ cathode material _{(Li (1-x):} Co (1-yz): Fe y: Ti z: (PO 4) (1-a)) and It contained a lithium negative electrode.

[0213] Figure 15 shows the use of t-butyldimethylsilyl trifluoromethanesulfonate as a stabilizer over several cycles, expressed as a percentage of the initial specific capacity during discharge maintained in a particular cycle. This is a comparison of capacity retention rates when not used. As can be appreciated from this figure, inclusion of a stabilizer improved cycle life.

Example 9
Characterization of battery cells containing stabilizers
[0214] Using the method of Example 1, for test battery cells containing different stabilizers dispersed in a conventional electrolyte (ethylene carbonate, ethyl methyl carbonate, and 1 M LiPF ₆ ), and conventional electrolysis The performance characteristics were measured for a control battery cell containing liquid but no stabilizer. FIG. 16 compares the capacity retention of battery cells over several cycles, expressed as a percentage of the initial specific capacity during discharge maintained in a particular cycle. Two different types of stabilizers were used. One type contained silicon and another type did not have silicon. The stabilizer concentration was about 2% by weight. As can be appreciated from this figure, including a silicon-containing stabilizer improves cycle life and reduces the initial discharge after 100 cycles compared to less than about 65% without the stabilizer. Maintained over 80% of capacity. In this example, the silicon-free stabilizer deteriorated in capacity retention to about 45% after 100 cycles.

(Example 10)
Characterization of battery cells containing stabilizers
[0215] Using the method of Example 1, performance characteristics were measured for silicon-containing stabilizers containing different numbers of silicon-carbon bonds. FIG. 17 is a comparison of specific capacities during discharge in the 50th cycle for battery cells containing a stabilizer. As can be appreciated from this figure, the inclusion of a stabilizer containing more than two silicon-carbon bonds is more important than the 50th cycle compared to stabilizers containing less than three silicon-carbon bonds. Caused a higher discharge capacity.

(Example 11)
Characterization of battery cells containing stabilizers
[0216] Using the method of Example 1, for a test battery cell comprising different silicon-containing stabilizers dispersed in a conventional electrolyte (ethylene carbonate, ethyl methyl carbonate, and 1 M LiPF ₆ ), and conventionally The performance characteristics were measured for a control battery cell containing the electrolyte solution but without the stabilizer. Each of the stabilizers tested included Si-O-A moieties (A = P, B, or Si). FIG. 18 compares the capacity retention of battery cells over several cycles, expressed as a percentage of the initial specific capacity during discharge maintained in a particular cycle. As can be appreciated from this figure, inclusion of each of the stabilizers containing Si-O-A moieties improved cycle life.

(Example 12)
Characterization of battery cells containing stabilizers
[0217] Using the method of Example 1, for a test battery cell comprising different silicon-containing stabilizers dispersed in a conventional electrolyte (ethylene carbonate, ethyl methyl carbonate, and 1 M LiPF ₆ ), and conventionally The performance characteristics were measured for a control battery cell containing the electrolyte solution but without the stabilizer. FIG. 19 is a comparison of specific capacities during discharge in the 100th cycle for battery cells. The stabilizer concentration was about 2% by weight. As can be appreciated from this figure, inclusion of a silicon-containing stabilizer improved the discharge capacity.

(Example 13)
Characterization of battery cells containing stabilizers
[0218] Using the method of Example 1, about 2 wt% tris (trimethylsilyl) phosphate ("TTSP") dispersed in a conventional electrolyte (ethylene carbonate, ethyl methyl carbonate, and 1M LiPF ₆ ). ) And as a battery cell containing conventional electrolytes but no stabilizer (“EC: EMC (1: 2), 1M LiPF ₆ ”). The performance characteristics were measured. To assess low temperature stability, cycling was performed at about 10 ° C., about 0 ° C., and about −10 ° C. after initial cycling at room temperature (25 ° C.). FIG. 20 is a comparison of specific capacities during discharge of battery cells over several cycles at different temperatures. As can be evaluated from this figure, the discharge capacity was improved at a temperature below room temperature by including a stabilizer.

(Example 14)
Characterization of battery cells containing stabilizers
[0219] Using the method of Example 1, the effectiveness of tris (trimethylsilyl) phosphate as a stabilizer was tested on various cathode materials at elevated temperatures up to about 50 ° C. FIG. 21 shows a battery cell containing about 2 wt% stabilizer (labeled “TTSP”) dispersed in a conventional electrolyte (ethylene carbonate, ethyl methyl carbonate, and 1M LiPF ₆ ), and The capacity retention rate in the 25th cycle was compared for battery cells containing conventional electrolytes but no stabilizer (labeled “EC: EMC (1: 2v), 1M LiPF ₆ )”. Is. As can be evaluated from this figure, the inclusion of a stabilizer improved the capacity retention for each positive electrode material.

(Example 15)
Characterization of battery cells containing stabilizers
[0220] A LiMn ₂ O ₄ positive electrode coating was produced in a half cell (containing Li metal as negative electrode) in a coin cell type assembly (CR2025, Hohsen). One cell contains a conventional electrolyte (ethylene carbonate, ethyl methyl carbonate, and 1M LiPF ₆ ) with tris (trimethylsilyl) phosphate (labeled “TTSP”) as a stabilizer and another cell. Included a conventional electrolyte without a stabilizer (labeled “EC: EMC (1: 2), 1M LiPF ₆ )”. The cells were held at 50 ° C. for about 10 hours at about 4.5V, about 4.9V, and about 5.1V, and their residual currents were measured. The results are shown in FIG. As can be appreciated from this figure, the cell containing tris (trimethylsilyl) phosphate has a lower residual current, which indicates reduced electrolyte decomposition.

(Example 16)
Characterization of battery cells containing stabilizers
[0221] Battery cells each including a LiMn _1.5 Ni _0.5 O ₄ positive electrode material and a graphite negative electrode (MCMB) were assembled using the method of Example 1. One cell contains a conventional electrolyte (ethylene carbonate, ethyl methyl carbonate, and 1M LiPF ₆ ) with tris (trimethylsilyl) phosphate (labeled “TTSP”) as a stabilizer and another cell. Included a conventional electrolyte without a stabilizer (labeled “EC: EMC (1: 2), 1M LiPF ₆ )”. The cell was cycled at a rate of about 0.1 C for several cycles and their coulomb efficiency was measured in all cycles and the results are shown in FIG. As can be appreciated from this figure, inclusion of tris (trimethylsilyl) phosphate improved coulomb efficiency.

(Example 17)
Characterization of battery cells containing stabilizers
[0222] Battery cells each containing a doped LiCoPO ₄ cathode material and a graphite anode (MCMB) were assembled using the method of Example 1. One cell contains a conventional electrolyte (ethylene carbonate, ethyl methyl carbonate, and 1M LiPF ₆ ) with tris (trimethylsilyl) phosphate (labeled “TTSP”) as a stabilizer and another cell. Included a conventional electrolyte without a stabilizer (labeled “EC: EMC (1: 2), 1M LiPF ₆ )”. The cell was first cycled at room temperature (25 ° C.) and then stored at about 50 ° C. for 8 days in a charged state. Subsequently, the cell was cooled to room temperature and cycled again. FIG. 24 compares the specific capacities during discharge over several cycles with and without the use of a stabilizer. As can be appreciated from this figure, the inclusion of tris (trimethylsilyl) phosphate improves the discharge capacity after storage at high temperatures, thereby enhancing the thermal stability of the electrolyte and / or battery cell. It became to show.

(Example 18)
Characterization of battery cells containing stabilizers
[0223] doped LiCoPO ₄ cathode material _{(Li (1-x):} Co (1-yz): (PO 4) (1-a) Fe y:: Ti z) including and graphite negative electrode (MCMB), respectively The battery cell was assembled using the method of Example 1. One cell contains a conventional electrolyte (ethylene carbonate, ethyl methyl carbonate, and 1M LiPF ₆ ) with tris (trimethylsilyl) phosphate (labeled “ttsp”) as a stabilizer and another cell. Included a conventional electrolyte without a stabilizer (labeled “EC: EMC (1: 2), 1M LiPF ₆ )”. A typical rate test was performed at the 101st cycle, and the rate performance of the battery cell was measured. FIG. 25 compares the capacity retention of battery cells at different charge and discharge rates, expressed as a percentage of the low rate (0.05 C) specific capacity maintained at a specific rate. As can be appreciated from this figure, inclusion of tris (trimethylsilyl) phosphate improved both rate performance during charge and discharge.

(Example 19)
Characterization of battery cells containing stabilizers
[0224] Battery cells each including a LiMn _1.5 Ni _0.5 O ₄ positive electrode material and a graphite negative electrode (MCMB) were assembled using the method of Example 1. One cell contains a conventional electrolyte (ethylene carbonate, ethyl methyl carbonate, and 1M LiPF ₆ ) with tris (trimethylsilyl) phosphate as a stabilizer, and another cell is a conventional one without a stabilizer. It contained an electrolyte (labeled “EC: EMC (1: 2), 1M LiPF ₆ ”). The cell was cycled at a rate of about 0.1 C for several cycles. FIG. 26 is a comparison of capacity retention rates with and without the use of a stabilizer. As can be appreciated from this figure, inclusion of tris (trimethylsilyl) phosphate improved capacity retention.

(Example 20)
Characterization of battery cells containing stabilizers
[0225] doped LiCoPO ₄ cathode material _{(Li (1-x):} Co (1-yz): (PO 4) (1-a) Fe y:: Ti z) including and graphite negative electrode (MCMB), respectively The battery cell was assembled using the method of Example 1. One cell contains a conventional electrolyte (ethylene carbonate, ethylmethyl carbonate, and 1M LiPF ₆ ) with about 2 wt% tris (trimethylsilyl) phosphate as a stabilizer, and another cell contains a stabilizer. (It is indicated as “EC: EMC (1: 2), 1M LiPF ₆ ”). The cell was cycled at room temperature (25 ° C.) and the voltage profile during these charges in the first and 100th cycles is shown in FIG. A higher voltage during charging indicates an increase in resistance. As can be assessed from this figure, inclusion of tris (trimethylsilyl) phosphate reduced cell resistance.

(Example 21)
Characterization of battery cells containing stabilizers
[0226] A half cell (containing Li metal as a negative electrode) was assembled using the method of Example 1. One cell received a conventional electrolyte (ethylene carbonate, ethyl methyl carbonate, and 1M LiPF ₆ ) having about 2 wt% tris (trimethylsilyl) phosphate (labeled “TTSP”) as a stabilizer. In addition, another cell contained a conventional electrolyte without a stabilizer (labeled “EC: EMC (1: 2), 1M LiPF ₆ )”. The cell is cycled at room temperature (25 ° C.) and these voltage profiles during discharge in the third cycle are shown in FIG. As can be assessed from this figure, inclusion of tris (trimethylsilyl) phosphate reduced cell resistance.

(Example 22)
Method for the formation and characterization of battery cells containing stabilizers
[0227] Battery cells were formed in a glove box filled with high purity argon (M-Braun, O2 and moisture content <0.1 ppm). First, poly (vinylidene fluoride) (Sigma Aldrich), carbon black (Super P Li, TIMCAL), and cathode material are mixed in 1-methyl-2-pyrrolidinone (Sigma Aldrich) and thus obtained. The slurry was deposited on an aluminum current collector and dried to form a positive electrode composition film. Lithium or graphite negative electrode was used. In the case of a graphite negative electrode, graphitic carbon is mixed with poly (vinylidene fluoride) (Sigma Aldrich), carbon black (Super P Li, TIMCAL) using 1-methyl-2-pyrrolidinone (Sigma Aldrich) as a solvent. The slurry thus obtained was deposited on a copper current collector and dried to form a negative electrode composition film. Each battery cell comprising a cathode material composition coating, Millipore glass fiber or polypropylene separator, and a lithium or graphite anode was assembled in a coin cell type assembly (CR2025, Hohsen). A cell with a Li negative electrode was tested in a Hohsen CR2032 cell. A conventional electrolyte was mixed with a stabilizer and added to the battery cell. The battery cells were sealed and cycled between specific voltage ranges for each positive electrode at a specific temperature (eg, room temperature or 25 ° C.). Table 1 shows the cycling voltage range for each positive electrode in the full cell. The cutoff voltage at the upper end is 0.05 V higher in the half cell than in the full cell.

(Example 23)
Characterization of battery cells containing stabilizers
[0228] Using the method of Example 22, for a test battery cell comprising different silicon-containing stabilizers dispersed in a conventional electrolyte (ethylene carbonate, ethyl methyl carbonate, and 1M LiPF ₆ ), and conventionally The performance characteristics were measured for a control battery cell containing the electrolyte solution but without the stabilizer. In this example, the positive electrode material is of the LMNO type. FIG. 29 compares the coulomb efficiency of battery cells in the first cycle. It can be appreciated that some OTMS additives performed better than the controls.

(Example 24)
Characterization of battery cells containing stabilizers
[0229] Using the method of Example 22, for test battery cells comprising different silicon-containing stabilizers dispersed in a conventional electrolyte (ethylene carbonate, ethyl methyl carbonate, and 1 M LiPF ₆ ), and conventionally The performance characteristics were measured for a control battery cell containing the electrolyte solution but without the stabilizer. In this example, the positive electrode material was LMNO type and the test was performed at room temperature. FIG. 30 compares the capacity retention of battery cells over several cycles, expressed as a percentage of the initial specific capacity during discharge maintained in a particular cycle. It can be appreciated that some OTMS additives performed better than the controls.

(Example 25)
Characterization of battery cells containing stabilizers
[0230] Using the method of Example 22, for a test battery cell comprising different silicon-containing stabilizers dispersed in a conventional electrolyte (ethylene carbonate, ethyl methyl carbonate, and 1 M LiPF ₆ ), and conventionally The performance characteristics were measured for a control battery cell containing the electrolyte solution but without the stabilizer. In this example, the positive electrode material was LMNO type and the test was performed at room temperature. FIG. 31 compares the capacity retention of battery cells over several cycles, expressed as a percentage of the initial specific capacity during discharge maintained in a particular cycle. It can be appreciated that some NTMS additives performed better than the controls.

(Example 26)
Characterization of battery cells containing stabilizers
[0231] Using the method of Example 22, for a test battery cell comprising different silicon-containing stabilizers dispersed in a conventional electrolyte (ethylene carbonate, ethyl methyl carbonate, and 1M LiPF ₆ ), and conventionally The performance characteristics were measured for a control battery cell containing the electrolyte solution but without the stabilizer. In this example, the positive electrode material was LMNO type and the test was performed at room temperature. FIG. 32 compares the coulomb efficiency of battery cells in the first cycle. Some TMS additives can be evaluated as performing better than the controls.

(Example 27)
Characterization of battery cells containing stabilizers
[0232] Using the method of Example 22, for a test battery cell comprising different silicon-containing stabilizers dispersed in a conventional electrolyte (ethylene carbonate, ethyl methyl carbonate, and 1M LiPF ₆ ), and conventionally The performance characteristics were measured for a control battery cell containing the electrolyte solution but without the stabilizer. In this example, the positive electrode material was LMNO type and the test was performed at room temperature. FIG. 33 compares the capacity retention rates of the battery cells over several cycles, expressed as a percentage of the initial specific capacity during discharge maintained in a particular cycle. Some TMS additives can be evaluated as performing better than the controls.

(Example 28)
Characterization of battery cells containing stabilizers
[0233] Using the method of Example 22, for a test battery cell comprising different silicon-containing stabilizers dispersed in a conventional electrolyte (ethylene carbonate, ethyl methyl carbonate, and 1 M LiPF ₆ ), and conventionally The performance characteristics were measured for a control battery cell containing the electrolyte solution but without the stabilizer. In this example, the positive electrode material was of the CM1 type. FIG. 34 compares the coulomb efficiency of battery cells in the first cycle. It can be appreciated that some OTMS additives performed better than the controls.

(Example 29)
Characterization of battery cells containing stabilizers
[0234] Using the method of Example 22, for a test battery cell comprising different silicon-containing stabilizers dispersed in a conventional electrolyte (ethylene carbonate, ethyl methyl carbonate, and 1 M LiPF ₆ ), and conventionally The performance characteristics were measured for a control battery cell containing the electrolyte solution but without the stabilizer. In this example, the positive electrode material was of the CM1 type. FIG. 35 compares the coulomb efficiency of battery cells in the first cycle. It can be appreciated that some OTMS additives performed better than the controls.

(Example 30)
Characterization of battery cells containing stabilizers
[0235] Using the method of Example 22, for a test battery cell comprising different silicon-containing stabilizers dispersed in a conventional electrolyte (ethylene carbonate, ethyl methyl carbonate, and 1 M LiPF ₆ ), and conventionally The performance characteristics were measured for a control battery cell containing the electrolyte solution but without the stabilizer. In this example, the positive electrode material was CM1 type, and the test was performed at room temperature. FIG. 36 compares the capacity retention of battery cells over several cycles, expressed as a percentage of the initial specific capacity during discharge maintained in a particular cycle. It can be appreciated that some OTMS additives performed better than the controls.

(Example 31)
Characterization of battery cells containing stabilizers
[0236] Using the method of Example 22, for test battery cells comprising different silicon-containing stabilizers dispersed in a conventional electrolyte (ethylene carbonate, ethyl methyl carbonate, and 1 M LiPF ₆ ), and conventionally The performance characteristics were measured for a control battery cell containing the electrolyte solution but without the stabilizer. In this example, the positive electrode material was CM1 type, and the test was performed at room temperature. FIG. 37 compares the capacity retention rates of battery cells over several cycles, expressed as a percentage of the initial specific capacity during discharge maintained in a particular cycle. It can be appreciated that some OTMS additives performed better than the controls.

(Example 32)
Characterization of battery cells containing stabilizers
[0237] Using the method of Example 22, for a test battery cell comprising different silicon-containing stabilizers dispersed in a conventional electrolyte (ethylene carbonate, ethyl methyl carbonate, and 1M LiPF ₆ ), and conventionally The performance characteristics were measured for a control battery cell containing the electrolyte solution but without the stabilizer. In this example, the positive electrode material was CM1 type, and the test was performed at room temperature. FIG. 38 compares the capacity retention of battery cells over several cycles, expressed as a percentage of the initial specific capacity during discharge maintained in a particular cycle. It can be appreciated that some NTMS additives performed better than the controls.

(Example 33)
Characterization of battery cells containing stabilizers
[0238] Using the method of Example 22, for a test battery cell comprising different silicon-containing stabilizers dispersed in a conventional electrolyte (ethylene carbonate, ethyl methyl carbonate, and 1 M LiPF ₆ ), and conventionally The performance characteristics were measured for a control battery cell containing the electrolyte solution but without the stabilizer. In this example, the positive electrode material was NMC type and the test was performed at high temperature. FIG. 39 compares the capacity retention rates of battery cells over several cycles, expressed as a percentage of the initial specific capacity during discharge maintained in a particular cycle. It can be evaluated that the OTMS additive performed better than the control.

(Example 34)
Characterization of battery cells containing stabilizers
[0239] Using the method of Example 22, for a test battery cell comprising different silicon-containing stabilizers dispersed in a conventional electrolyte (ethylene carbonate, ethyl methyl carbonate, and 1 M LiPF ₆ ), and conventionally The performance characteristics were measured for a control battery cell containing the electrolyte solution but without the stabilizer. In this example, the positive electrode material was NMC type and the test was performed at high temperature. FIG. 40 compares the capacity retention of battery cells over several cycles, expressed as a percentage of the initial specific capacity during discharge maintained in a particular cycle. It can be evaluated that the OTMS additive performed better than the control.

(Example 35)
Characterization of battery cells containing stabilizers
[0240] Using the method of Example 22, for test battery cells comprising different silicon-containing stabilizers dispersed in a conventional electrolyte (ethylene carbonate, ethyl methyl carbonate, and 1M LiPF ₆ ), and conventionally The performance characteristics were measured for a control battery cell containing the electrolyte solution but without the stabilizer. In this example, the positive electrode material was of the OLO type and the test was performed at room temperature. FIG. 41 compares the capacity retention rates of battery cells over several cycles, expressed as a percentage of the initial specific capacity during discharge maintained in a particular cycle. It can be evaluated that the OTMS additive performed better than the control.

(Example 36)
Characterization of battery cells containing stabilizers
[0241] Using the method of Example 22, for a test battery cell comprising different silicon-containing stabilizers dispersed in a conventional electrolyte (ethylene carbonate, ethyl methyl carbonate, and 1 M LiPF ₆ ), and conventionally The performance characteristics were measured for a control battery cell containing the electrolyte solution but without the stabilizer. In this example, the positive electrode material was of the OLO type and the test was performed at a high temperature. FIG. 42 compares the capacity retention of battery cells over several cycles, expressed as a percentage of the initial specific capacity during discharge maintained in a particular cycle. It can be evaluated that the OTMS additive performed better than the control.

(Example 36)
Characterization of battery cells containing stabilizers
[0242] Using the method of Example 22, for a test battery cell comprising different silicon-containing stabilizers dispersed in a conventional electrolyte (ethylene carbonate, ethyl methyl carbonate, and 1 M LiPF ₆ ), and conventionally The performance characteristics were measured for a control battery cell containing the electrolyte solution but without the stabilizer. In this example, the positive electrode material was of the OLO type and the test was performed at room temperature. FIG. 43 compares the capacity retention rates of battery cells over several cycles, expressed as a percentage of the initial specific capacity during discharge maintained in a particular cycle. It can be evaluated that the OTMS additive performed better than the control.

(Example 37)
Characterization of battery cells containing stabilizers
[0243] Using the method of Example 22, for a test battery cell comprising different silicon-containing stabilizers dispersed in a conventional electrolyte (ethylene carbonate, ethyl methyl carbonate, and 1M LiPF ₆ ), and conventionally The performance characteristics were measured for a control battery cell containing the electrolyte solution but without the stabilizer. In this example, the positive electrode material was of the OLO type and the test was performed at room temperature. FIG. 44 compares the energy efficiency of battery cells over several cycles. It can be evaluated that the OTMS additive performed better than the control.

(Example 38)
Characterization of battery cells containing stabilizers
[0244] Using the method of Example 22, for a test battery cell comprising different silicon-containing stabilizers dispersed in a conventional electrolyte (ethylene carbonate, ethyl methyl carbonate, and 1M LiPF ₆ ), and conventionally The performance characteristics were measured for a control battery cell containing the electrolyte solution but without the stabilizer. In this example, the positive electrode material was of the LMNO type and the test was performed at a high temperature. FIG. 45 compares the capacity retention of battery cells over several cycles, expressed as a percentage of the initial specific capacity during discharge maintained in a particular cycle. It can be evaluated that the OTMS additive performed better than the control.

(Example 39)
Characterization of battery cells containing stabilizers
[0245] Using the method of Example 22, for a test battery cell comprising different silicon-containing stabilizers dispersed in a conventional electrolyte (ethylene carbonate, ethyl methyl carbonate, and 1 M LiPF ₆ ), and conventionally The performance characteristics were measured for a control battery cell containing the electrolyte solution but without the stabilizer. In this example, the electrode material was of the LMO type and the test was performed at a high temperature. FIG. 46 compares the capacity retention of battery cells over several cycles, expressed as a percentage of the initial specific capacity during discharge maintained in a particular cycle. It can be evaluated that the OTMS additive performed better than the control.

[0246] While this invention has been described in terms of specific embodiments, various modifications may be made without departing from the true spirit and scope of this invention as defined by the appended claims. One skilled in the art should understand that things may be substituted. In addition, many modifications may be made to a particular situation, material, composition, method, or process to adapt to the purpose, spirit, and scope of the invention. All such modifications are intended to be within the scope of the claims appended hereto. In particular, while the methods disclosed herein have been described with respect to particular operations performed in a particular order, these operations can be combined or further divided without departing from the teachings of the present invention. Or rearranged to form an equivalent method. Therefore, unless otherwise specified herein, the order and grouping of operations does not limit the invention.

Claims (20)

A negative electrode comprising a negative electrode active material characterized by a first specific capacity;
A positive electrode comprising a positive electrode active material characterized by a second specific capacity, wherein the first specific capacity and the second specific capacity are matched such that the battery is characterized by a rated charge voltage of greater than about 4.2V A positive electrode,
Lithium salt, non-aqueous solvent, and formula (I)

Wherein R ₁ , R ₂ , and R ₃ are each independently a substituted and unsubstituted C ₁ -C ₂₀ alkyl group, a substituted and unsubstituted C ₁ -C ₂₀ alkenyl group, a substituted and unsubstituted C ₁ -C ₂₀ alkynyl group, and it is selected from the group consisting of C ₅ -C ₂₀ aryl group substituted and unsubstituted,
X is nitrogen or oxygen;
Y is a hydride group, halo group, hydroxy group, thio group, alkyl group, alkenyl group, alkynyl group, aryl group, iminyl group, alkoxy group, alkenoxy group, alkynoxy group, aryloxy group, carboxy group, alkylcarbonyloxy Group, alkenylcarbonyloxy group, alkynylcarbonyloxy group, arylcarbonyloxy group, alkylthio group, alkenylthio group, alkynylthio group, arylthio group, cyano group, N-substituted amino group, alkylcarbonylamino group, N-substituted alkylcarbonyl group Amino group, alkenylcarbonylamino group, N-substituted alkenylcarbonylamino group, alkynylcarbonylamino group, N-substituted alkynylcarbonylamino group, arylcarbonylamino group, and N-substituted arylcarbonylamino group Group, a boron-containing group, an aluminum-containing group, a silicon-containing group is selected from the group consisting of phosphorus-containing groups, and sulfur-containing groups. )
An electrolyte solution containing a compound represented by:
Including the battery.   The positive electrode active material has a specific capacity of at least about 10 mAh / (g of active material) when discharged at a current of about 0.01 C over a voltage range of about 4.9 V to about 4.2 V. The battery according to claim 1.   The positive electrode active material has a specific capacity of at least about 40 mAh / (g of active material) when discharged at a current of about 0.01 C over a voltage range of about 4.9 V to about 4.2 V. The battery according to claim 1.   The positive electrode active material has a specific capacity of at least about 100 mAh / (g of active material) when discharged at a current of about 0.01 C over a voltage range of about 4.9 V to about 4.2 V. The battery according to claim 1.   The battery of claim 1 having a Coulomb efficiency of at least about 90% from the first cycle to 100 cycles.   The battery of claim 1, having a Coulomb efficiency of at least about 90% from the first cycle to 100 cycles when operating in an environment at a temperature greater than about 50 ° C.   The battery of claim 1 having a Coulomb efficiency of at least about 90% from the first cycle to 100 cycles when the battery is at a temperature of about 50C.   The battery according to claim 1, wherein the positive electrode active material includes a material selected from the group consisting of nickel, manganese, and cobalt.   The battery according to claim 1, wherein the positive electrode active material includes a spinel structure lithium metal oxide, a layered structure lithium metal oxide, or a lithium-excess layered structure lithium metal oxide.   The battery according to claim 1, wherein the positive electrode active material includes a lithium metal phosphate. Lithium salt,
A non-aqueous solvent;
Formula (I)

Wherein R ₁ , R ₂ , and R ₃ are each independently a substituted and unsubstituted C ₁ -C ₂₀ alkyl group, a substituted and unsubstituted C ₁ -C ₂₀ alkenyl group, a substituted and unsubstituted C ₁ -C ₂₀ alkynyl group, and it is selected from the group consisting of C ₅ -C ₂₀ aryl group substituted and unsubstituted,
X is nitrogen or oxygen;
Y is a hydride group, halo group, hydroxy group, thio group, alkyl group, alkenyl group, alkynyl group, aryl group, iminyl group, alkoxy group, alkenoxy group, alkynoxy group, aryloxy group, carboxy group, alkylcarbonyloxy Group, alkenylcarbonyloxy group, alkynylcarbonyloxy group, arylcarbonyloxy group, alkylthio group, alkenylthio group, alkynylthio group, arylthio group, cyano group, N-substituted amino group, alkylcarbonylamino group, N-substituted alkylcarbonyl group Amino group, alkenylcarbonylamino group, N-substituted alkenylcarbonylamino group, alkynylcarbonylamino group, N-substituted alkynylcarbonylamino group, arylcarbonylamino group, and N-substituted arylcarbonylamino group Group, a boron-containing group, an aluminum-containing group, a silicon-containing group is selected from the group consisting of phosphorus-containing groups, and sulfur-containing groups. )
And a compound represented by
An electrolyte for a high-voltage battery, characterized by electrochemical stability at a voltage greater than about 4.2 V in a high-voltage battery.   The electrolyte of claim 1 further characterized by electrochemical stability when the battery operates in an environment at a temperature of about 50 ° C.   The electrolyte of claim 1 further characterized by electrochemical stability when the battery is at a temperature of about 50 ° C.   The electrolyte of claim 1, characterized by electrochemical stability at a voltage greater than about 4.5 V in a high voltage battery.   The electrolyte of claim 1, characterized by electrochemical stability at a voltage greater than about 5.0 V in a high voltage battery. Lithium salt,
A non-aqueous solvent;
Formula (I)

Wherein R ₁ , R ₂ , and R ₃ are each independently a substituted and unsubstituted C ₁ -C ₂₀ alkyl group, a substituted and unsubstituted C ₁ -C ₂₀ alkenyl group, a substituted and unsubstituted C _1- C ₂₀ alkynyl group, and is selected from the group consisting of substituted and unsubstituted C ₅ -C ₂₀ aryl group,
X is nitrogen or oxygen;
Y is a hydride group, halo group, hydroxy group, thio group, alkyl group, alkenyl group, alkynyl group, aryl group, iminyl group, alkoxy group, alkenoxy group, alkynoxy group, aryloxy group, carboxy group, alkylcarbonyloxy Group, alkenylcarbonyloxy group, alkynylcarbonyloxy group, arylcarbonyloxy group, alkylthio group, alkenylthio group, alkynylthio group, arylthio group, cyano group, N-substituted amino group, alkylcarbonylamino group, N-substituted alkylcarbonyl group Amino group, alkenylcarbonylamino group, N-substituted alkenylcarbonylamino group, alkynylcarbonylamino group, N-substituted alkynylcarbonylamino group, arylcarbonylamino group, and N-substituted arylcarbonylamino group Group, a boron-containing group, an aluminum-containing group, a silicon-containing group, phosphorus-containing group, and is selected from the group consisting of sulfur-containing group)
Preparing an electrolyte solution comprising: a compound represented by:
Providing a negative electrode comprising a negative electrode active material characterized by a first specific capacity;
Providing a positive electrode comprising a positive electrode active material characterized by a second specific capacity, wherein the battery is characterized by a rated charge voltage of greater than about 4.2 V; The specific capacity is matched,
Incorporating a negative electrode, a positive electrode and optionally a separator into the electrochemical cell;
Adding electrolyte to the cell;
Sealing the cell to form a high voltage battery;
A method for producing a high voltage battery.   The positive electrode active material is characterized by a specific capacity of at least about 10 mAh / (g of active material) when discharged at a current of about 0.01 C over a voltage range of about 4.9 V to about 4.2 V. 16. The method according to 16.   The method of claim 16, wherein the positive electrode active material comprises a material selected from the group consisting of nickel, manganese, and cobalt.   The method according to claim 16, wherein the positive electrode active material comprises spinel structure lithium metal oxide, layered structure lithium metal oxide, or lithium-excess layered structure lithium metal oxide.   The method of claim 16, wherein the positive electrode active material comprises a lithium metal phosphate.

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