TW474041B - Sulfite additives for nonaqueous electrolyte rechargeable cells - Google Patents

Abstract

A lithium ion electrochemical cell having high charge/discharge capacity, long cycle life and exhibiting a reduced first cycle irreversible capacity, is described. The stated benefits are realized by the addition of at least one sulfite additive to an electrolyte comprising an alkali metal salt dissolved in a solvent mixture that includes ethylene carbonate, dimethyl carbonate, ethylmethyl carbonate and diethyl carbonate. The preferred additive is an alkyl sulfite compound.

Description

474041 5. Description of the invention (1) References to related applications The scope of this application is based on the US Provisional Application Serial No. 0 6/1 1 7, 10 5 and it was filed on January 2, 1999. 5th. BACKGROUND OF THE INVENTION The present invention relates to metal electrochemical cells, and more particularly to rechargeable alkaline metal batteries. In more detail, the present invention relates to a lithium ion electrochemical cell activated by an electrolyte having an additive that achieves a high charge / discharge capacity, a long cycle life, and a reduction in the irreversible capacity of the first cycle. According to the method of the present invention, a preferred additive for activating the electrolytic solution is a sulfite compound. Alkaline metal rechargeable batteries typically include a carbonaceous anode and a lithiated cathode. Due to the high potential of the cathode material in Li-ion batteries (Li Co 02 vs. Li / Li + up to 4.3 V), the carbonaceous anode material has low potential (graphite vs. Li / Li + 0.01 V), The electrolyte solvent system is limited. Carbonate solvents are generally used in lithium-ion battery electrolytes because they have high oxidative stability for commonly used lithiated cathode materials and good kinetic stability for carbonaceous anode materials. For best performance (high rate capability and long cycle life), solvent systems containing a mixture of cyclic carbonates (high dielectric constant solvents) and low linear carbonates (low viscosity solvents) are generally used in industrial batteries. It is reported that a battery based on a carbonic acid electrolyte provides more than 1,000 charge / discharge cycles at room temperature. US Patent Application Serial No. 0 9/1 3 3, 7 9 9 (assigned herein by reference and incorporated herein) proposes the use of a quaternary mixture of an organic carbonate solvent for lithium in an activated electrolyte Ion battery, which can

O: \ 62 \ 62923.ptd Page 4 474041 V. Description of the invention (2) Discharge below-20 ° C, even if it is as low as-40 ° C, it shows good cycle performance. The quaternary solvent system includes 1,2-ethylene carbonate (EC), dimethyl carbonate (DMC), osmium ethyl ester (EMC), and diethyl carbonate (DEC). Lithium-ion battery design is generally a trade-off based on the target battery application in one necessary improvement area to another. Use the above quaternary solvent electrolyte instead of the commonly used ones; .it solvent electrolyte (such as 1. OM LiPF6 / EC: DMC: 30: 70 (volume / volume), freezing point at -1 1 ° C) The low-temperature cycling capability is obtained at the cost of increasing the irreversible capacity of the first cycle between initial charging observations (for 1.0M LiPF6 / EC: DMC: EMC: DEC = 45: 22: 24.8: 8.2 is 65 mAh / g graphite, while for 1.0M LiPF6 / EC: DMC = 3 0: 7 0 is 35 mAh / g). Because of the irreversible capacity of the first cycle, lithium ion batteries are generally limited by the cathode. Because all the lithium ions that shuttle between the anode and the cathode during charging and discharging are originally from the lithiated cathode, the larger the irreversible capacity in the first cycle, the lower the battery capacity in the subsequent cycles, and the lower the battery efficiency. Therefore, it is preferable to reduce or even eliminate the first cycle irreversible capacity in the lithium ion battery while maintaining the low temperature cycling capability of the battery. According to the present invention, these objects are obtained by providing an organic sulfite in a quaternary solvent electrolyte. Compared with the same quaternary solvent electrolyte activated battery without the sulphurous acid additive, the lithium ion battery used to wait for the electrolyte has a lower first-cycle irreversible capacity. As a result, batteries including sulfite additives showed higher subsequent cycle capacity than control batteries. The cyclability of the battery of the present invention at room temperature and low temperature (such as as low as about-40 ° C) is as good as the activation of the quaternary electrolyte without sulfite additive. Summary of invention

O: \ 62 \ 62923.ptd Page 5 474041 5. Description of the invention (3) Generally, we are familiar with the fact that when a lithium ion battery constructed with a carbon anode is initially charged with a potential under discharge conditions to charge the battery, a passivation film is formed on the anode surface. , Will lose some permanent capacity. This permanent capacity loss is called the first cycle irreversible capacity. However, the film formation process relies heavily on the reactivity of the electrolyte components at the battery charge potential. The electrochemical performance of the passivation film also depends on the chemical composition of the surface film. For alkali metal systems, the formation of surface films is inevitable, especially for lithium metal anodes and carbon anodes with lithium in it, because lithium has a relatively low potential and high reactivity for organic electrolytes. An ideal surface film (known as a solid-electrolyte mesophase (SE I) should be electrically insulating and capable of conducting ions. Although most alkali metals (especially lithium electrochemical systems) are thin enough to meet the first need, the second need is difficult to obtain. The resistance of these films is not negligible because the surface layer is generated to cause unacceptable polarization during charging and discharging of the lithium-ion battery, creating impedance in the battery. On the other hand, if the SEI film is conductive, due to the lithiated carbon electrode With a low potential, the electrolyte decomposition reaction on the anode surface does not stop.

Therefore, the components of the electrolyte have a considerable influence on the discharge efficiency of the alkali metal system, especially the permanent capacity loss of the battery. For example, when 1.0 μM LiPF6 / EC: DMO 3 0: 70 is used to activate the battery, the irreversible capacity of the first cycle is close to 35 mA / g of graphite. But with 1.0M

LiPF6 / EC: DM C: EMC: DEC = 45: 22: 24.8: 8.2 As electrolyte, under the same cycling conditions, the irreversible capacity of the first cycle was found to be approximately 65 mA / g. In addition, lithium ion batteries activated with a binary solvent electrolyte of 1,2-ethylene carbonate and dimethyl carbonate cannot be cycled at less than about -1 ° C. previously

O: \ 62 \ 62923.ptd Page 6 474041 V. Description of the invention (4) The quaternary solvent electrolyte of the patent application referred to enables the lithium-ion battery to cycle at a lower temperature, showing that it can provide a better cycle efficiency at an acceptable cycle efficiency. Wide temperature applications. Therefore, it is highly desirable to reduce the irreversible capacity of the first cycle while maintaining the benefits of lithium-ion batteries operating at a low temperature of about -40 ° C. According to the method of the present invention, this object is achieved by adding a phosphoromorphate additive to the above-mentioned quaternary solvent electrolyte. Furthermore, the present invention can be extended to other non-aqueous organic electrolyte systems, such as binary and ternary solvent systems and electrolyte systems other than mixtures containing linear or cyclic carbonates. For example, linear or cyclic ethers or esters can also be used as electrolyte components. Although the exact reason for the improvement observed is not clear, it can be assumed that during the initial lithiation, the sulfite additive competes with the electrolyte components present to react on the carbon anode surface. Therefore, the SE I film formed is more electrically insulating than the film formed without a sulfite additive, and therefore, the lithiated carbon electrode is better protected under the reaction of other electrolyte components. Therefore, to obtain a lower first cycle irreversible capacity ° With reference to the following detailed description, these and other objects of the present invention will be more apparent to those skilled in the art. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An electrochemical battery manufactured according to the present invention includes an anode active material selected from Group IA, IIA, or IIIB of the Periodic Table of Elements, including lithium, sodium, potassium, and the like. Preferred anode active materials include lithium. In electrochemical battery systems, the anode electrode includes a material capable of introducing and removing an alkali metal, preferably lithium. Preferred carbonaceous anodes include any form of carbon that can reversibly retain lithium species, such as coke, graphite, acetylene ink, carbon black,

O: \ 62 \ 62923.ptd page 7 474041, description of the invention (5) vitrified Π. Ishiguro has a relatively high retention-lithium capacity, so it is particularly beneficial to consider the form of carbon, which hinders the use of high-quality material fibers, because the mechanical properties of the fiber make it a rigid electrode that can withstand repeated charging / discharging ^ . In addition, the high surface area of carbon fibers allows fast electrical rates. A preferred carbonaceous material for use in a chemical battery anode is described in U.S. Patent No. 5,443,928 to Takeuchi et al., Which is divided by reference and incorporated herein by reference. Denier battery anodes are manufactured by mixing about 90 to 97% by weight of graphite and about 3 to 10% by weight of adhesive material, preferably a fluororesin powder, such as polytetrafluoroethylene = polyvinylidene fluoride (F), poly Ethylenetetrafluoroethylene y Polyamine and polyimide and mixtures thereof. The electrode activation mix is provided on It: Ϊ electrical appliances, such as by casting, ®, rolling or other methods of active mixing ° provided on nickel, impervious steel or copper foil or wire mesh. The pole element further has the same expansion sheet or anode material as the anode current collector, such as nickel, and is integrally formed by welding. And the battery case is contacted by welding with a conductive metal in the device. In addition, carbonaceous electrodes can be formed into a number of other geometries, such as cylindrical, cylindrical, or pellet-shaped, & change the design of the low cell. Cathode cathodes preferably include lithiated materials that are stable in the air and easy to handle. Examples of such air-stabilized lithiated cathode materials include the oxides, sulfides, selenides, and tellurides of the metals vanadium, aluminum, chromium, copper, molybdenum, niobium, iron, nickel, cobalt, and manganese. Preferred oxides include UNi02, UMn202, io02 L iC0. 92Sn 0.82 and L iC 0 x x ix 02. Lithium active material 474041 before making electrode for electrochemical cell

Better with conductive additives. Carbon black and / or stone, black: Electrical additives include acetylene black and metal as the main channel. When s is mixed with the above active materials, powdered outer spoons also include rf electric diluents. Such as Lu, Ming, Titanium and * Lu steel. In addition, the electrode includes a resin adhesive, preferably in a powder form, such as ptfe, pvdf, polyamine, polyimide, and a mixture thereof. ^ The battery is discharged, and the cathode lithium ion is recharged by applying an externally generated anode. A recharging potential is applied to produce alkali metal ions from the anion * β and enter the carbonaceous anode through the electrolyte, so that the percentage is extremely small. Households {Dr. 1} · ρ Hall pay Ll; the electrode may have an X value between 0.1 and 1. The battery is then supplied with a potential and discharged in the normal manner.

A kind of battery structure is intercalated with carbonaceous materials with active alkali materials before the anode is added to the battery. In this case, the cathode body may be solid, including, but not limited to, manganese dioxide, silver oxide vanadium, silver copper oxide vanadium, titanium disulfide, copper oxide copper sulfide, iron sulfide, iron disulfide, and carbon fluoride. However, this method has been hampered by issues related to handling lithium lithiated carbon outside the battery.

The storage battery of the present invention includes an isolation layer that provides physical separation between the anode and the cathode active electrode. The isolation layer is an electrically insulating material that prevents an electrical short between electrodes. The isolation layer material does not chemically react with the anode and the cathode active material, is not reactive with the electrolyte solution, and is insoluble in the electrolyte solution. Moreover, the separation layer material has sufficient porosity to allow the electrolyte to flow through during the electrochemical reaction of the battery. The isolation layer is generally sheet-shaped and is placed between the anode and the cathode. This is the case when the anode is folded in a serpentine structure and has multiple cathode plates inserted in the middle of the anode stack and received in the battery case, or when the electrode composition is rolled into a ^ -shaped A cylindrical π rubber roller "device. .

474041 V. Description of the invention (7) Illustrative separation layer materials include woven fabrics of fluoropolymer fibers made of poly (ethylenetetrafluoroethylene) and poly (ethylene) difluoroethylene, which can be used alone or with fluoropolymers. Laminated porous film. Other suitable insulating layer materials include non-woven glass, polypropylene, polyethylene, fiberglass materials, ceramics, PTFE film commercially obtained under the name of ΙΤΕχ [Che mp last company], and commercially available in CELGARD [Celanese pUstic

Company, Inc.)] and films obtained under the name DEXIGLAS [C.H. Dexter, Div., Des. Due to the high potential of the cathode material (up to 4.3 V for u / u + for Lii x CO2) and the low potential of the anode material (0.01 V for graphite / Li / U +), the solution solvent system: Activated alkali metal electrochemical cells (especially fully charged lithium-ion batteries) are extremely limited. According to the present invention, rhenium is composed of non-aqueous electrolyte in a non-aqueous solvent, and is more preferably composed of an alkali metal salt dissolved in rhenium) and at least one ring-based carbonate vinegar, which is selected from dimethyl carbonate (DMC), . t (DPC), thorium carbonate · Γ ethyl Se (DEC), dipropyl carbonate: (EMC), methyl propyl carbonate (MPC) and propyl carbonate (PC), carbon tritium mixture t, ring system The carbonated vinegar is selected from the group consisting of ethylene carbonate and ethylene carbonate. And, acid breaking U2-butylene vinegar (BC) and that Θ and its compounds. Yichuan will use the right ground #private battery chemistry institute Xitang Iridium ★ organic anti-acid S will be used for this high-grade chemical solution ^ Solvent solvent system, because the cathode material exhibition ~ ~, good display of anode material Kinetic Determination & Solution Packing: DMC: EMC: DE; t = Mixed

474041 V. Description of the invention (8). The optimal volume percentage ranges for various carbonate solvents include about 10% to about 50% EC, about 5% to about 75% DMC, about 5% to about 50% EMC, and about 3% to about 45% DEC. The electrolyte containing the quaternary carbonate mixture shows a freezing point below -50 ° C. The lithium ion battery activated by this mixture has good cycle performance at room temperature, and good discharge and discharge at temperatures below -20 ° C. / Charging cycle performance. Lithium salts used as mediators to transport alkali metal ions from anode to cathode and back again include LiPF6, LiBF4, Li AsF6, LiSbF6, LiC104, Li A1C14, LiGaCl4, LiC (S02CF3) 3, LiN03, LiN (S02CF3) 2, LiSCN , Li03SCF2CF3, LiC6F5S03, Li02CCF3, LiS03F, LiB (C6H5) 4 and LiCF3S03 and mixtures thereof. The applicable salt concentration is generally between about 0.8 to 1.5 moles. The present invention provides at least one organic sulfite additive in the electrolyte. The sulfite additive has the general formula VOS (= 0) (OR2), wherein R1 and R2 may be the same or different, and the two may be a hydrogen atom or an organic group containing 1 to 12 carbon atoms. Η, R1 has at least the structure (R3) (R4) (R5) C-, at least R3 is an aromatic substituent or an unsaturated organic group or an inorganic group, and if any of the retention groups of R4 and R5 is a saturated organic Group, the saturated organic group contains 1 to 11 carbon atoms. The following substances will be found to be most effective when used as electrolyte additives, which include propylene disulfite, methyl sulfite, ethyl sulfite, ethyl benzyl sulfite, propyl sulfite, hydrazine, and butyl sulfite. • Bentyl esters, pentyl sulfite, thiocyanate, sulfite, propylene disulfide, ethyl sulfite, allyl sulfide, propyl sulfite, acetic acid, butyl sulfite, butyl sulfide, pentyl sulfite • Allyl S purpose, sulfurous acid

O: \ 62 \ 62923.ptd Page 11 474041 V. Description of the invention (9)-Monosulfonium S, monothionyl sulfite, monopropyl sulfite, monopentyl sulfite, monopentyl sulfite Monopropyl sulfate, monobenzyl sulfite, dibenzyl ester and mixtures thereof. The above compounds are used for demonstration only and are not intended to be limiting. Known in this art, Gu Yi 5 can bear the sulfite compounds from the above general formula range, and the Hua Ren 2 will be used as an electrolyte additive to reduce the voltage delay. Although the compound is not willing to be bound by some specific mechanisms, it is believed that since the acid and vinegar additive contains at least one c (sp2 or 叩 3) -c (sp3) bond unit ^ sulfur unsaturated 'and the bond unit is C (sp3) The carbon is directly connected to -0S02 ~ Guanji ', so it is easy to form a bond between oxygen and at least one R1 and ^. The 2 furnace acid vinegar intermediate can effectively compete with other electrolyte solvents or solutes, react with 1 and generate Sulfite (such as lithium sulfite), or lithium salt of sulfate reduction products on the anode surface. Feng Ya In fact, it is believed that due to the equilibrium reaction on the anode surface, the lithium salt of the sulfite (sulfite) reduction product on the anode surface provides charge delocalization. This equilibrium makes it easy for turtle ions to migrate from one molecule to another via a lithium ion exchange mechanism. This achieves beneficial ion conduction. Therefore, it can be said that the organic sulfite compound is more effective than other alkyl sulfites and cyclic sulfite (such as 1,2-ethylene sulfite and 1,2-propylene sulfite). Other solvents in the electrolyte compete for a thin film that is more ionically conductive and electrically insulating. Therefore, it is believed that the chemical composition and possible morphology of the surface protective layer of the carbonaceous electrode will change from the accompanying advantages to the performance advantages of the battery cycle ring. The battery device described herein is preferably in the form of a "wound element battery". That is, the anodes, cathodes, and separators manufactured in

Page 12 474041 V. Description of the invention (10) ^ 1 2 "In the middle winding" so that the anode is located outside the roller and is in electrical contact with the battery case in the negative case structure. Insert the wound battery pack into a metal case of a suitable size with appropriate upper and lower insulators. The metal case may include stainless steel, soft steel, nickel soft steel, titanium, or aluminum, but it is not limited to this, as long as the metal material and battery components Just compatible. The battery head includes a metal disc body. The first hole of the disc body receives the glass-gold seal / terminal pin-shaped feed slot, and the second hole is used to fill the electrolyte. The TA soil used is a corrosion-resistant type with up to about 50% by weight silicon, such as CABAL 12, preferably 3 scoops or FUSITE 425 or FUSITE 435. Positive terminal needle feed troughs include titanium, but molybdenum, aluminum, nickel alloy or stainless steel can also be used. Batteries, including other components of electrochemical cells, are compatible, and are resistant to needles. Lightning leads are welded to positive terminals in glass-to-metal seals. Ten battery heads are welded to thunder. Μι * Seven kinds of I—f% # μ t 3 on the shell of the electrode wire. Subsequently, a stainless steel filled battery was electrolytically sealed and welded with at least one of the above-mentioned sulfurous acid additives, and a negative shell battery was assembled and filled on the filled hole. structure. Those skilled in the art should understand that the non-standard battery of the present invention is preferably manufactured with a positive shell structure. The off-track electrochemical system can also limit the concentration of sulfite additives used to about 0.20 mol / l. If the additive concentration is less than 0.001 mol / l, the effect will not be obvious. On the other hand, such as, 40 · 0 〇 丨 Moore / liter, there are Moore / liter, due to the formation of a thicker anode surface Guobao additive concentration is greater than about 0.20 low, the harmful effects of higher internal resistance of the battery will eliminate the film And the electrolyte conductivity drop should be understood, and those skilled in this art can not: + the beneficial effects of additives.

Open the scope of patent application for this invention 474041 V. Make various improvements to this invention within the spirit and scope of the invention description (π) Page 14

Claims (1)

474041 ^ π ^^ 先 丰 _ Case No. 89109249_ Year "Month and Day Amendment Six Application Patent Scope 1. An electrochemical cell includes: a) a kind of negative electrode intervened by a test metal; b) a kind of active material including an electrode A positive electrode intervened by an alkali metal; c) a non-aqueous electrolyte that activates the negative electrode and the positive electrode; and d) a sulfite additive provided in the electrolytic solution. 2 · Electrochemistry according to item 1 of the scope of the patent application Battery, wherein the sulfite additive has the formula: R1 OS (= 0) (OR2), the formula has at least one unsaturated hydrocarbon containing a C (sp2 or sp3) -C (sp3) bond unit, and the bond unit C (sp3) carbon directly connected to a 0S02-functional group. 3. The electrochemical cell according to item 1 of the scope of patent application, wherein in the formula R1 0S (= 0) (0R2), R1 and R2 may be the same or different And both may be a hydrogen atom or an organic group containing 1 to 12 carbon atoms, and if R2 is fluorene and at least R3 is an aromatic substituent or an unsaturated organic group or an inorganic group, at least R1 has Structure (foot 3) (1? 4) (1 ^) (:-, and if any of the retaining groups of 1 ^ and 1? 5 are saturated In the case of an organic group, the saturated organic group contains 1 to 11 carbon atoms. J; IL 4. The electrochemical cell according to item 1 of the patent application scope, wherein the additive is selected from the group consisting of diallyl sulfite, Europium sulphate • benzyl sulphate, ethyl sulphite • propyl sulphite • T ester, butyl sulphite • T ester, pentyl sulphate • sulphate, methyl sulphite • allyl s purpose, ethyl sulphite s purpose, propylene allyl acid, butyl allyl sulfite s purpose, pentyl allyl sulfite, monomethyl sulfite, monoethyl sulfite, monopropyl sulfite, monobutyl sulfite A group consisting of esters, monopentyl sulfite, monoallyl sulfite, monomethyl sulfite, and di-T sulfite and mixtures thereof. 5. An electrochemical cell according to item 1 of the scope of patent application, wherein Sulphur O: \ 62 \ 62923.ptc Page 15 474041 Amendment No. 89109249 6. The scope of patent application The ester additives are present at about 0 · 0 0 1 mol / liter (M) to about 0.2 0 mol / liter. . 6. The electrochemical cell according to item 1 of the patent application scope, wherein the electrolyte includes a quaternary, non-aqueous carbonate solvent mixture. 7. The electrochemical cell according to item 1 of the application, wherein the electrolyte includes at least one linear carbonate selected from the group consisting of dimethyl carbonate, diethyl carbonate, dipropyl carbonate, methyl ethyl ester, and carbonic acid. A group consisting of methyl propyl ester and ethyl propyl carbonate and their mixtures. 8. An electrochemical cell according to item 7 of the patent application, wherein the electrolyte includes at least three linear carbonates. 9. An electrochemical cell according to item 1 of the scope of patent application, wherein the electrolyte includes at least one cyclic carbonate, selected from the group consisting of 1,2-ethylene carbonate, 1,2-propylene carbonate, and 1,2-carbonate, A group consisting of 2-butylene and 1,2-vinyl carbonate and mixtures thereof. Wherein the electrolytic ethyl ester and carbon wherein the carbon 10 is an electrochemical cell according to item 1 of the scope of the patent application, the liquid includes 1,2-ethylene carbonate, dimethyl carbonate, and diethyl carbonate. 1 1. According to the scope of the patent application, the electrochemical battery acid 1,2-ethylidene is in the range of about 10 vol% to about 50 vol%, and the difluorene carbonate is in the range of about 5 vol%. In the range of about 75% by volume, the methyl ethyl ester is in the range of about 5% by volume to about 50% by volume, and the diethyl carbonate is in the range of about 3% by volume to about 45% by volume. 12. The electrochemical cell according to item 1 of the scope of patent application, wherein the electrolytic solution includes an alkali metal salt selected from the group consisting of LiPF6, LiBF4, LiAsF6, O: \ 62 \ 62923.ptc Page 16 474041 _ Case No. 89109249_W year (January __ VI) Patent application scope LiSbF6, LiC104, LiAlCl4, LiGaCl4, LiN03, LiC (S02CF3) 3, LiN (S02CF3) 2, LiSCN, Li03SCF2CF3, LiC6F5S03, Li02CCF3, LiS03F, LiB (C6H5) 4, and LiCF3S03 and mixtures thereof. 1 3. The electrochemical cell according to item 12 of the scope of the patent application, wherein the alkali metal is lithium. 1 4. The electrochemical cell according to item 1 of the patent application scope, wherein the negative electrode includes a negative electrode active material selected from the group consisting of coke, carbon black, stone black, acetylene black, carbon fiber, glassy carbon black, and mixtures thereof. 1 5. The electrochemical cell according to item 1 of the patent application scope, wherein the negative electrode active material is mixed with a fluororesin adhesive. 1 6. The electrochemical cell according to item 1 of the patent application scope, wherein the positive electrode includes a positive electrode active material, and the option is Group consisting of free vanadium, titanium, chromium, copper, molybdenum, niobium, iron, nickel, cobalt and manganese, and their mixed lithiated oxides, lithiated sulfides, lithiated compounds, and chemical compounds. 1 7. According to application The electrochemical cell in the range of item 16, wherein the positive electrode active material is mixed with a fluorinated resin adhesive. 1 8. The electrochemical cell in accordance with the range of item 16 in the patent application, wherein the positive electrode active material is in combination with a conductive additive. Mixed, the conductive additive is selected from the group consisting of acetylene black, carbon black, graphite, nickel powder, aluminum powder, titanium powder, and stainless steel powder, and mixtures thereof. 1 9. An electrochemical cell comprising: a) a kind of Negative electrode with lithium intervention; b) a positive electrode including electrode active material and lithium intervention; O: \ 62 \ 62923.ptc Page 17 474041 Amendment No. 89109249 6. Scope of patent application c) An electrolyte for activating anode and cathode, the electrolyte includes alkali metal salt, which is soluble in carbonic acid 1, 2-A quaternary, non-aqueous carbonate solvent mixture of ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate and diethyl carbonate; d) a sulfite additive provided in the electrolyte. 2 0. The electrochemical cell according to item 19 of the scope of patent application, wherein the sulfite additive has the following formula: R10S (= 0) (0 R2), the formula has at least one containing C (sp2 or sp3) -C (sp3) An unsaturated hydrocarbon of a bond unit having a C (sp3) carbon directly connected to an OS02-functional group. 2 1. The electrochemical cell according to item 19 of the scope of patent application, wherein in the formula 1 ^ 03 (= 0) (01 ^ 2), R1 and R2 may be the same or different, and the two may be a hydrogen atom or containing An organic group of 1 to 12 carbon atoms, and if R2 is closed, and at least R3 is an aromatic substituent or an unsaturated organic or inorganic group, at least R1 has the structure (R3) (R4) (R5) C- And if any of the retaining groups of R4 and R5 is a saturated organic group, the saturated organic group contains 1 to 11 carbon atoms. 2 2. The electrochemical cell according to item 19 of the scope of patent application, wherein the sulfite additive is selected from the group consisting of diallyl sulfite, methyl sulfite Ester, ethyl benzyl sulfite, propyl benzyl sulfite, butyl sulfite, T ester, pentyl sulfite, methyl allyl sulfite, ethyl allyl sulfite, propyl sulfite Allyl ester, butyl allyl sulfite, pentyl sulfite, monomethyl sulfite, monoethyl sulfite, monopropyl sulfite, monobutyl sulfite, monopentyl sulfite , Monoallyl sulfite, monobenzyl sulfite and difluorenyl sulfite and mixtures thereof. 2 3. The electrochemical cell according to item 19 of the patent application, wherein the carbon O: \ 62 \ 62923.ptc Page 18 474041 Case No. 89109249 > Year " Month Amendment VI. Patent Application Scope Acid 1,2 ethylene is in the range of about 10% by volume to about 50% by volume The dimethyl carbonate is in a range of about 5 vol% to about 75 vol%, the methyl ethyl ester is in a range of about 5 vol% to about 50 vol%, and the diethyl carbonate is in a range of about 5 vol% to about 50 vol%. Within the range of about 3% by volume to about 45% by volume. 2 4. The electrochemical cell according to item 19 of the scope of patent application, wherein the electrolyte includes an alkali metal salt selected from the group consisting of LiPF6, LiBF4, LiAsF6, LiSbF6, LiC104, Li A1C14, LiGaCl4, LiN03, LiC (S02CF 3) 3. LiN (S02CF3) 2, LiSCN, Li03SCF2CF3, LiC6F5S03, Li02 CCF3, LiS03F, LiB (C6H5) 4 * LiCF3S03 and mixtures thereof. 2 5. — An electrochemical cell comprising: a) — a pole of a carbonaceous material capable of allowing lithium to intervene; b) — a cathode containing the beginning of oxidation; and c) a nonaqueous electrolysis that activates the anode and cathode The non-aqueous electrolyte includes a sulfite additive to provide lithium sulfite or a salt of a sulfite (salt) reduction product on the surface of a lithium-incorporated anode (related to electrolysis). 26. A method for providing an electrochemical cell, comprising the following steps: a) providing a negative electrode interposed by a metal test; b) providing a positive electrode including an electrode active material and interposed by an alkali metal; c) using a non-aqueous electrolyte Activating the negative and positive electrodes; and d) providing a sulfite additive in the electrolyte. 2 7. The method according to item 26 of the scope of patent application, which includes providing a formula: O: \ 62 \ 62923.ptc Page 19 474041 Amendment No. 89109249 Six. Sulfuric acid S additive for patent application scope R10S (= 0) (0 R2), this formula has at least one containing C (sp2 or sp3 ) -C (sp3) unsaturated hydrocarbon unit, and the bond unit has a C (sp3) carbon directly connected to a 0S02-functional group. 2 8. The method according to item 26 of the scope of patent application, wherein in the general formula R1 · 0S (= 0) (0R2), R1 and R2 may be the same or different, and the two may be hydrogen atoms or contain 1 to 12 An organic group of carbon atoms, and if R2 is closed, and at least R3 is an aromatic substituent or an unsaturated organic or inorganic group, at least R1 has the structure (R3) (R4) (R5) C-, and if When any of the retaining groups of R4 and R5 is a saturated organic group, the saturated organic group contains 1 to 11 carbon atoms. 29. The method according to item 26 of the scope of patent application, which comprises selecting a sulfite additive, which is selected from the group consisting of diallyl sulfite, methyl thiosulfate, ethyl sulfite, ethyl sulfide, Propyl sulfate, butyl sulfate, butyl sulfite, pentyl sulfite, ammonium sulfite, fluorene sulfide, allyl, ethene sulfite, propylene sulfite, butyl sulfite Propyl ester, pentyl allyl sulfite, monomethyl sulfite, monoethyl sulfite, monopropyl sulfite, monobutyl sulfite, monopentyl sulfite, monoallyl sulfite, A group consisting of mono-T sulfate and dibenzyl sulfite and mixtures thereof. 30. The method according to item 26 of the patent application range, wherein the sulfite additive is present in the electrolytic solution at about 0.01 mol / liter to about 0.2 mol / liter. 3 1. A method according to item 26 of the scope of patent application, which includes providing an electrolytic solution comprising a quaternary, non-aqueous carbonate dissolved mixture. 32. The method according to item 26 of the patent application scope, wherein the electrolyte includes at least one linear carbonate selected from the group consisting of dimethyl carbonate, diethyl carbonate O: \ 62 \ 62923.ptc Page 20 474041 Amendment No. 89109249 Six. Patent applications: esters, dipropyl carbonate, methyl carbonate, ethyl acetate, methyl • propyl carbonate, and ethyl • propyl carbonate and mixtures thereof group. β 3 3. The method according to item 32 of the application, wherein the electrolyte includes at least three linear carbonates. _ 3 4. The method according to item 26 of the scope of patent application, wherein the electrolyte includes at least one cyclic carbonate, which is selected from the group consisting of 1,2-ethylene carbonate, 1,2-propylene carbonate, and 1 A group consisting of 1,2-butylene ester and 1,2-vinylene carbonate and mixtures thereof. 35. The method according to item 26 of the scope of patent application, wherein the electrolytic solution includes 1,2-ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate, and diethyl carbonate. 36. The method according to item 35 of the scope of patent application, wherein the 1,2-ethylene carbonate is in the range of about 10 vol% to about 50 vol%, and the dimethyl carbonate is in the range of about 5 vol. % To about 75% by volume, the methyl ethyl ester is in the range of about 5% to about 50% by volume, and the diethyl carbonate is in the range of about 3% by volume to about 45% by volume. . _ 3 7. The method according to item 26 of the scope of patent application, wherein the electrolyte includes an alkali metal salt selected from the group consisting of LiPF6, LiBF4, LiAsF6, LiSbF6, LiC104, LiAlCl4, LiGaCl4, LiN02, LiC (S 02C F3 ) 3, LiN (S02CF3) 2, LiSCN, Li03SCF2CF3 'LiC6F5S03, Li02CCF3, LiS03F, LiB (C6H5) 4 * LiCF3S03 and mixtures thereof. _ 38. The method according to item 26 of the scope of patent application, which includes providing alkali metal lithium. 39. The method according to item 26 of the patent application scope, which includes providing a positive electrode O: \ 62 \ 62923.ptc Page 21 474041 Case No. 89109249 °! On the 6th, the amendments to the patent application scope of the positive electrode active material, the positive electrode active material is selected from the , Nickel, cobalt, and manganese, and a mixture of lithiated oxides, lithiated sulfides, lithiated selenides, and lithiated tellurides. 40. The method according to item 26 of the patent application scope, comprising providing a negative electrode including a negative electrode active material selected from the group consisting of coke, carbon black, graphite, acetylene black, carbon black fibers, and glassy carbon black and mixtures thereof Composition group O: \ 62 \ 62923.ptc Page 22