Electrolyte for a lithium battery and a lithium battery comprising the same

The present invention relates to an electrolyte for a lithium battery and a lithium battery comprising the same. The electrolyte includes a non-aqueous organic solvent, a lithium salt, and a first additive capable of forming a chelating complex with a transition metal and which is stable at voltages ranging from about 2.5 to about 4.8 V.

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Description
CROSS REFERENCE TO RELATED APPLICATION

This application claims priority to and the benefit of Korean Patent Application No. 110-2005-0016691 filed in the Korean Intellectual Property Office on Feb. 28, 2005, the entire content of which is incorporated herein by reference.

FIELD OF THE INVENTION

The present invention relates to an electrolyte for a lithium battery and a lithium battery comprising the same, and more particularly, to an electrolyte which improves battery safety.

BACKGROUND OF THE INVENTION

Portable electronic devices are becoming smaller and lighter due to advancements in the high-tech electronic industry. As a result, portable electronic devices are increasingly being used. The increased need for batteries having high energy density for use as power sources for these portable electronic devices has led to recent research into lithium secondary batteries.

Lithium secondary batteries have average discharge potentials of about 4 V, and more particularly 3.7 V. These lithium secondary batteries are essential to the digital generation because they are indispensable energy sources for portable digital devices such as the “3C” devices, i.e. cellular telephones, notebook computers, and camcorders, as well as other portable electronic devices.

Research has also been conducted on batteries to develop effective safety characteristics such as the prevention of overcharge. When a battery is overcharged, excess lithium ions are deposited on the positive electrode, and excess lithium ions are inserted into the negative electrode, making the positive and negative electrodes thermally unstable. An explosion may occur due to the decomposition of the electrolytic organic solvent causing thermal runaway which can seriously decrease battery safety.

To overcome these problems, an aromatic compound, such as an oxidation-reduction agent, or “redox shuttle additive,” has been added to the electrolyte. For example, U.S. Pat. No. 5,709,968 to Shimizu discloses the use of a benzene compound, such as 2,4-difluoroanisole, in a non-aqueous lithium ion secondary battery to prevent thermal runaway resulting from overcharge current. Also, U.S. Pat. No. 5,879,834 to Mao discloses the use of electrochemically polymerized aromatic compounds, such as biphenyl, 3-chlorothiophene, furan, etc., to improve battery safety by increasing the internal resistance of the battery during unusual overvoltage conditions.

Redox shuttle additives quickly increase the temperature inside the battery by the heat produced by the oxidation-reduction reaction. In addition, the additive closes the pores of the separator by quickly and uniformly fusing the separator to inhibit overcharge reactions. The polymerization reaction of these redox shuttle additives consumes the overcharge current, thereby improving battery safety.

However, the need for high capacity batteries is increasing, and these redox shuttle additives cannot provide the high level of safety required of such high capacity batteries. Therefore, a need exists for an electrolyte capable of preventing overcharge and ensuring battery safety.

SUMMARY OF THE INVENTION

In one embodiment of the present invention, a lithium battery electrolyte imparts improved battery safety.

In another embodiment of the present invention, a lithium battery comprises an electrolyte which imparts improved battery safety.

One embodiment of the electrolyte for a lithium battery includes a non-aqueous organic solvent, a lithium salt, and an additive which is stable at voltages ranging from about 2.5 to about 4.8 V. The additive is capable of forming a chelating complex with a transition metal.

In another embodiment of the present invention, a lithium battery includes an electrolyte having a non-aqueous organic solvent, a lithium salt, and an additive which is stable at voltages ranging from about 2.5 to about 4.8 V. The electrolyte additive is capable of forming a chelating complex with a transition metal. The battery further comprises a positive electrode and a negative electrode. The positive electrode comprises a positive active material capable of intercalating and deintercalating lithium ions. The negative electrode comprises an active material selected from the group consisting of materials capable of intercalating/deintercalating lithium ions, lithium metals, lithium-containing alloys, and materials capable of forming lithium-containing compounds by reversibly reacting lithium.

BRIEF DESCRIPTION OF THE DRAWINGS

These and other features and advantages of the present invention will be better understood by reference to the following detailed description when considered in conjunction with the accompanying drawings, in which:

FIG. 1 is a cross-sectional view of a lithium battery according to one embodiment of the present invention;

FIG. 2 is a graph of the voltammetry measurements of a lithium secondary battery prepared according to Experimental Example 1; and

FIG. 3 is a graph of the current, temperature, and voltage characteristics, measured at 1.5 C, during overcharging of lithium batteries prepared according to Example 2 and Comparative Example 2.

DETAILED DESCRIPTION OF THE PRESENT INVENTION

Exemplary embodiments of the present invention will now be described with reference to the accompanying drawings. However, one of ordinary skill in the art understands that various modifications may be made to the described embodiments, and that the invention is not limited to the described embodiments. Rather, the embodiments are described for illustrative purposes only.

The present invention relates to an electrolyte for a lithium battery. FIG. 1 is a cross-sectional view of a non-aqueous lithium secondary battery according to one embodiment of the present invention. The battery 1 comprises an electrode assembly 8 contained within a battery case 10. The electrode assembly 8 includes a positive electrode 2, a negative electrode 4 and a separator 6 positioned between the positive and negative electrodes 2 and 4, respectively. The positive and negative electrodes 2 and 4, respectively, comprise active materials capable of intercalating and deintercalating lithium ions. The separator can comprise polyethylene, polypropylene, or a combination thereof.

An electrolyte is injected into the battery case 10 and impregnated into the positive and negative electrodes 2 and 4, and the separator 6. The battery case 10 is sealed with a cap plate 12 and a sealing gasket 14. The cap plate 12 has a safety vent (not shown) for releasing overpressure and comprises a lead plate 24 and an insulating plate 26 positioned between the lead plate 24 and the cap plate 12. A positive tab 18 is attached to the positive electrode 2, and a negative tab 20 is attached to the negative electrode 4. The negative terminal 22 is electrically connected to the electrode assembly 8 through the negative tab 20. The battery case 10 acting as a positive terminal is electrically connected to the electrode assembly 8 through the positive tab 18.

In lithium secondary batteries, temperature increases abruptly during overcharge due to incorrect operation or break-down of the battery, or when short circuits occur due to a defect in battery design. This abrupt increase in temperature results in thermal runaway. During overcharge, excess lithium ions are released from the positive electrode and deposited on the surface of the negative electrode, rendering the positive and negative electrodes unstable. As a result, exothermic reactions rapidly increase the temperature inside the battery, causing thermal runaway and generating fire and smoke. Such exothermic reactions may include pyrolysis of the electrolyte, reactions between the electrolyte and lithium, oxidation reactions of the electrolyte and the positive electrode, reactions between the electrolyte and oxygen gas generated from the pyrolysis of the positive active material, etc.

In light of these problems, various additives have been researched, including overcharge-inhibiting additives and additives for improving battery safety when stored at high temperatures. However, although these additives serve their intended objective, they have other shortcomings. For example, overcharge-inhibiting additives, such as phenyl acetate, decrease the safety of the battery when stored at high temperatures. Additionally, metal impurities, which remain after battery fabrication, cause voltage drops.

The electrolytes according to one embodiment of the present invention include first additives which trap the metals or metal impurities released from the positive electrode during overcharge or high temperate storage. These first additives are stable at voltages ranging from about 2.5 to about 4.8 V, and are capable of forming chelating complexes with chelating metals. The first additive traps metals, thereby preventing voltage drops and decreasing safety risks caused by deposition of metal on the negative electrode, which can result in short circuits. In particular, the first additives ensure battery safety when stored at high temperatures.

The first additive is capable of forming a chelating complex and comprises a compound represented by Formulas 1 to 3 and mixtures thereof:

In Formulas 1 through 3, R1, R2, R3, R4, R5, and R6 may be either the same or different compounds. However, at least one of R1 through R3 and at least one of R4 through R6 is a compound represented by the formula AxR′, where A is selected from the group consisting of N, O, P and S, x is 0 or 1, and R′ is selected from the group consisting of CN, C1 to C15 linear alkyls, C1 to C15 linear carboxyls, C1 to C15 branch alkyls and C1 to C15 branch carboxyls. The remaining R1 through R6 groups each comprise a material selected from the group consisting of H, halogens, C1 to C15 alkyls and C6 to C15 aryls. In the Formulas 1 through 3, n is an integer ranging from 0 to 10, and n1 is an integer ranging from 0 to 15. When n1 is an odd number, a is 1, and when n1 is an even number, a is either ½ or 1.

Non-limiting examples of first additives suitable for use in the present invention include the compounds represented by the following Formulas 4 to 26 and mixtures thereof:

In the above Formulas 4 to 26, Me is methyl and Ph is phenyl.

In one embodiment, the first additive is present in an amount ranging from about 0.1 to about 10 wt % based on the total weight of the electrolyte. In another embodiment, the first additive is present in an amount ranging from about 1 to about 5 wt % based on the total weight of the electrolyte. In yet another embodiment, the first additive is present in an amount ranging from about 3 to about 5 wt % based on the total weight of the electrolyte. When the first additive is present in an amount less than about 0.1 wt %, the effect of the addition is negligible. When the first additive is present in an amount more than about 10 wt %, cycle life upon charge and discharge deteriorates.

The electrolyte may further include a second additive capable of releasing a transition metal from the positive electrode. The combination of the first additive, which is capable of forming a chelating complex, with the second additive substantially converts overcharge mode, caused by an internal short circuit, to shut-down mode, resulting in guaranteed safety during overcharge.

The second additive can comprise an ester-based compound. Non-limiting examples of such an ester-based compound include phenyl acetate, benzyl benzoate, ethyl acetate, 1-naphthyl acetate, 2-chromanone, and ethyl propionate.

In one embodiment, the second additive is present in an amount ranging from about 1 to about 10 parts by weight based on 100 parts by weight of the electrolyte. In another embodiment, the second additive is present in an amount ranging from about 1 to about 7 parts by weight based on 100 parts by weight of the electrolyte. In yet another embodiment, the second additive is present in an amount ranging from about 3 to 5 parts by weight based on 100 parts by weight of the electrolyte. When the second additive is present in an amount less than about 1 part by weight, overcharge is not substantially inhibited. When the second additive is present in an amount more than about 10 parts by weight, cycle life may deteriorate.

The electrolyte further includes a non-aqueous organic solvent and a lithium salt. The lithium salt supplies the lithium ions in the battery, making the basic operation of the lithium battery possible. The non-aqueous organic solvent is the medium for mobilizing the ions capable of participating in the electrochemical reaction.

Non-limiting examples of suitable lithium salts include LiPF6, LiBF4, LiSbF6, LiAsF6, LiClO4, LiCF3SO3, Li(CF3SO2)2N, LiC4F9SO3, LiAlO4, LiAlCl4, LiN(CxF2x+1SO2)(CyF2y+1SO2) wherein x and y are natural numbers, LiCl, Lil and mixtures thereof.

In one embodiment, the concentration of the lithium salt ranges from about 0.6 to about 2.0 M. In another embodiment, the concentration of the lithium salt ranges from about 0.7 to about 1.6 M. When the concentration of the lithium salt is less than about 0.6 M, electrolyte performance deteriorates due to its ionic conductivity. When the concentration of the lithium salt is greater than about 2.0 M, the mobility of the lithium ions decreases due to increased electrolyte viscosity.

The non-aqueous organic solvent may include carbonates, esters, ethers, ketones and mixtures thereof. Non-limiting examples of suitable carbonates include dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethylpropyl carbonate (EPC), methylethyl carbonate (MEC), ethylene carbonate (EC), propylene carbonate (PC), and butylene carbonate (BC). Non-limiting examples of esters include n-methyl acetate, n-ethyl acetate, n-propyl acetate, and the like.

In one embodiment, the organic solvent includes a mixture of a chain carbonate and a cyclic carbonate. In this embodiment, the volume ratio of the cyclic carbonate to the chain carbonate ranges from about 1:1 to about 1:9. When the volume ratio of the cyclic carbonate to the chain carbonate is within this range, and the mixture is used as an electrolyte, electrolyte performance is improved.

In another embodiment, the electrolyte may further comprise a mixture of carbonate solvents and aromatic hydrocarbon solvents, such as those represented by Formula 27:

In Formula 27, R10 is a compound selected from the group consisting of halogens and C1 to C10 alkyls, and q is an integer ranging from 0 to 6. Non-limiting examples of aromatic hydrocarbon solvents suitable for use in the present invention include benzene, fluorobenzene, toluene, trifluorotoluene, chlorobenzene, and xylene.

The volume ratio of carbonate solvents to aromatic hydrocarbon solvents ranges from about 1:1 to about 30:1. When the volume ratio of carbonate solvents to aromatic hydrocarbon solvents is within this range, and the mixture is used as an electrolyte, electrolyte performance is enhanced.

The electrolyte may further include a third additive comprising a compound selected from the group consisting of vinylene carbonate, divinylsulfone, ethylene sulfite and carbonates having substituents selected from the group consisting of halogens, cyano (CN) groups, and nitro (NO2) groups. This third additive improves the electrochemical characteristics of the battery. For example, the third additive inhibits swelling at high temperatures and increases capacity, cycle life, and low-temperature properties. In one embodiment, the third additive comprises a carbonate additive. Non-limiting examples of suitable carbonate additives include ethylene carbonate derivatives, such as fluoroethylene carbonate, and the compounds represented by Formula 28:

In Formula 28, X1 is selected from the group consisting of halogens, cyano (CN) groups, and nitro (NO2) groups.

The electrolyte of the present invention is prepared by adding the additives and the lithium salt to a non-aqueous organic solvent. Alternatively, the additives may be added to a solution of the lithium salt dissolved in the organic solvent. The order of addition of the lithium salt and the additives is not important.

In one embodiment of the present invention, a lithium battery includes the inventive electrolyte. In this embodiment, the positive active material comprises a lithiated intercalation compound, which is capable of intercalating/deintercalating lithium. The negative active material is selected from the group consisting of carbonaceous materials capable of intercalating/deintercalating lithium, lithium metals, lithium-containing alloys and materials capable of reversibly forming lithium-containing compounds by reacting lithium.

The lithium battery may be either a lithium primary battery or a lithium secondary battery.

The lithium batteries of the present invention have improved overcharge inhibition properties when compared with batteries having conventional non-aqueous electrolytes.

The following Examples, Experimental Examples and Comparative Examples further illustrate the present invention and are presented for illustrative purposes only. However, the present invention is not limited by these Examples, Experimental Examples and Comparative Examples.

COMPARATIVE EXAMPLE 1

94 g of LiCoO2 as a positive active material, 3 g of Super P (acetylene black) as a conductive agent, and 3 g of polyvinylidenefluoride (PVdF) as a binder were mixed in N-methyl-2-pyrrolidone (NMP) to prepare a positive electrode slurry. The slurry was coated on aluminum foil having a width of 4.9 cm and a thickness of 147 μm. The slurry coated aluminum foil was then dried, compressed, and cut to form a positive electrode.

90 g of mesocarbon fiber (MCF from PETROCA company) as a negative active material and 10 g of PVdF as a binder were mixed to prepare a negative electrode slurry. The slurry was coated on copper foil having a width of 5.1 cm and a thickness of 178 μm. The slurry coated copper foil was then dried, compressed and cut to form a negative electrode.

A polyethylene film separator was positioned between the positive and negative electrodes, and the positive and negative electrodes and the separator were then wound to form an electrode assembly. The electrode assembly was placed in a battery case and an electrolyte was injected into the case under pressure, thus completing the lithium secondary battery cell.

The electrolyte was prepared by dissolving 1 M LiPF6 in a mixed solvent of ethylene carbonate, ethylmethyl carbonate, dimethyl carbonate, and fluorobenzene. The volume ratio of ethylene carbonate:ethylmethyl carbonate:dimethyl carbonate: fluorobenzene was 3:5:1:1. Chlorotoluene was added in an amount of 10 parts by weight based on 100 parts by weight of the prepared electrolyte, and phenyl acetate was added in an amount of 7 parts by weight.

Three battery cells, No. 1, No. 2 and No. 3, were prepared according to Comparative Example 1. Open Circuit Voltage (OCV), Internal Resistance (IR), and battery thickness of each cell were measured after standard charge and after placement at 85° C. for 4 hours. These measurements are shown in Table 1.

TABLE 1 After standard After placement charge at 85° C. for 4 hours Cell IR Thickness IR Thickness No. OCV(V) (mohm) (mm) OCV(V) (mohm) (mm) No. 1 4.15 51.3 5.65 1.00 430.0 8.00 No. 2 4.14 52.7 5.57 0.80 457.4 7.50 No. 3 4.14 51.8 5.59 1.10 347.5 7.80

As shown in Table 1, when only phenyl acetate is used as an additive, after placement of the cells at high temperature, the OCV of each cell decreased significantly and battery thickness increased remarkably. This indicates that gas was generated inside the battery, causing serious swelling.

COMPARATIVE EXAMPLE 2

A lithium secondary battery was prepared as in Comparative Example 1, except that phenyl acetate was not used.

EXPERIMENTAL EXAMPLE 1

A working electrode was prepared using glassy carbon, and a reference electrode and counter electrode was prepared using lithium metal. Cyclic voltammetry of succino nitrile was then measured three times at a scanning rate of 0.5 mV/second. The results are shown in FIG. 2. As shown in FIG. 2, succino nitrile did not show an oxidation-reduction peak between 2.5 and 4.8 V, indicating that this compound is stable in this voltage range.

EXPERIMENTAL EXAMPLE 2

A positive electrode was prepared as in Comparative Example 1 and subjected to the standard charge conditions. The positive electrode was then dipped in an electrolyte solution. Subsequently, phenyl acetate and a first additive capable of forming a chelating complex were added to the positive electrode, and the positive electrode was then stored at 85° C. for four hours. Table 2 lists the first additive used and the color of the electrolyte solution.

TABLE 2 Color after storage at Initial color 85° C. for 4 hours Example 1 Transparent Deep orange Succino nitrile Transparent pale yellow Aceto nitrile Transparent Light pink Valero nitrile Transparent Light pink 3-ethoxy-propionitrile Transparent Light pink Ethylene glycol diacrylate Transparent Pink 1,2- Pale yellow Yellow bis(diphenylphosphino)ethane 1,2-dibromoethane Transparent Pale orange Ethylenediamine Yellow Deep brown Tetraethylenediamine Yellow Deep brown

Table 2 shows that after cobalt was released a complex was formed resulting in a change of color. From the results shown in Table 2, amine-based compounds are expected to react with the electrolyte solution to cause the color to change to deep brown.

EXAMPLE 1

A lithium secondary battery was fabricated as in Comparative Example 1, except that the electrolyte was prepared by adding succino nitrile to a solution of 1 M LiPF6 dissolved in a mixed solvent of ethylene carbonate, ethylmethyl carbonate, dimethyl carbonate and fluorobenzene. The volume ratio of ethylene carbonate: ethylmethyl carbonate:dimethyl carbonate:fluorobenzene was 3:5:5:1. The succino nitrile was added in an amount of 5 wt % based on the total weight of electrolyte.

EXAMPLE 2

A lithium secondary battery was fabricated as in Example 1, except that the electrolyte was prepared by adding succino nitrile and phenyl acetate to a solution of 1 M LiPF6 dissolved in a mixed solvent of ethylene carbonate, ethylmethyl carbonate, dimethyl carbonate and fluorobenzene. The volume ratio of ethylene carbonate: ethylmethyl carbonate:dimethyl carbonate:fluorobenzene was 3:5:5:1. The succino nitrile was added in an amount of 5 wt % based on the total weight of electrolyte, and the phenyl acetate was added in an amount of 3 parts by weight based on 100 parts by weight of the electrolyte.

EXAMPLE 3

A lithium secondary battery was fabricated as in Example 1, except that 3-ethoxy-propionitrile (EPN) was used instead of succino nitrile. The 3-epoxy-propionitrile was added in an amount of 5 wt % based on the total weight of electrolyte.

EXAMPLE 4

A lithium secondary battery was fabricated as in Example 1, except that ethylene glycol diacrylate (EGDA) was used instead of succino nitrile. The ethylene glycol diacrylate was added in an amount of 5 wt % based on the total weight of electrolyte.

EXAMPLE 5

A lithium secondary battery was fabricated as in Example 1, except that 1,2-bis(diphenylphosphino)ethane (DPPE) was used instead of succino nitrile. The 1,2-bis(diphenylphosphino)ethane was added in an amount of 5 wt % based on the total weight of electrolyte.

EXAMPLE 6

A lithium secondary battery was fabricated as in Example 1, except that 1,2-dibromoethane (DBE) was used instead of succino nitrile. The 1,2-dibromoethane was added in an amount of 5 wt % based on the total weight of electrolyte.

The lithium battery cells prepared according to Example 2 and Comparative Example 1 were overcharged at 1.5 C, and voltage and temperature were measured according to operating time. These measurements are shown in FIG. 3. As shown in FIG. 3, the lithium battery cell prepared according to Comparative Example 1, using only phenyl acetate as an additive, exhibited unstable voltage according to operating time, and the battery temperature was very high indicating poor battery safety. On the contrary, the lithium battery cell prepared according to Example 2, using phenyl acetate and succino nitrile, exhibited uniform operating voltage and the battery temperature was lower than that of Comparative Example 1, indicating improved battery safety.

The battery cells of Examples 1 to 6 and Comparative Examples 1 and 2 were stored at 85° C. for 4 hours. The battery cells of Examples 1 to 6 and Comparative Examples 1 and 2 were each separately overcharged. Overcharge was performed fully charging each cell to 4.2 V. Lead wires were prepared by resistant-welding a nickel tab to respective terminals. The lead wires were connected to charge-discharge equipment, and the battery cell was overcharged to 1.5 C (1.6 A)/12 V under constant current/constant voltage. After reaching 12 V, current was applied for 2.5 hours. During overcharge, the firing and explosion of cells were measured. These measurements are shown in Table 3. In Table 3, safety at overcharge is reported as follows:

L0: good, L1: leakage, L2: flash, L2: flame, L3: smoke, L4: ignition, L5: explosion.

TABLE 3 Additive Amount of capable of phenyl forming acetate Standard Placement chelating Amount (parts by capacity at high complex (%) weight) (mAh) temperature Overcharge Com. Ex. 2 — — 0 1083 OK L5 Com. Ex. 1 — — 7 1060 NG L0 Ex. 1 succino 5 0 1070 OK L3 nitrile Ex. 2 succino 5 3 1060 OK L0 nitrile Ex. 3 EPN 5 0 1088 OK L4 Ex. 4 EGDA 5 0 1051 OK L3 Ex. 5 DPPE 5 0 1048 OK L4 Ex. 6 DBE 5 0 1062 OK L5

As shown in Table 3, Example 2, in which succino nitrile and phenyl acetate were used exhibited good characteristics after high temperature storage and exhibited safety at overcharge. Examples 3 to 6, in which no phenyl acetate was used, exhibited satisfactory characteristics after high temperature storage and exhibited improved safety properties compared to Comparative Example 2, in which no additive was used. However, Examples 3 to 6 did not exhibit safety levels near L0.

Comparative Example 2, in which no additive was used, satisfied requirements for high temperature storage, but showed poor safety during overcharge. Comparative Example 1, in which only phenyl acetate was used as an additive, showed good safety at overcharge but poor performance after high temperature storage.

The battery cells according to Example 2 and Comparative Example 2 were subjected to standard charge, after which the OCV, IR, and battery thickness were measured. The battery cells were then stored at 85° C. for 4 hours, after which the OCV, IR, and battery thickness (t) were measured again. The battery thickness (t) was measured at 85° C. and at room temperature. These measurements are reported in Table 4.

Table 4 also reports the capacity of each cell after standard charge-discharge (STD_DC). In addition, Table 4 reports the discharge capacity of each cell measured after storage at high temperature and immediately cooling (ret(DC)). Finally, Table 4 reports the capacity of each cell measured after storage at high temperature, discharging, and then charging-discharging (rec(DC)). In Table 4, ret(DC) indicates charge capacity maintenance and rec(DC) indicates capacity maintenance after storage at high temperature.

TABLE 4 After placing at 85° C. After standard for 4 hours charge t (mm, STD OCV IR t OCV IR t (mm, Room DC ret(DC) rec(DC) (V) (mohm) (mm) (V) (mohm) 85° C.) temp.) (mAh) (mAh) (mAh) Ex. 2 4.15 48.6 5.67 4.11 59.8 6.13 5.85 1053.4 944.2 959.2 (No. 1) Ex. 2 4.15 48.1 5.69 4.12 58.1 6.27 5.88 1063.5 975.3 991.9 (No. 2) Ex. 2 4.18 48.8 5.72 4.12 59.8 6.12 5.91 1061.2 959.0 966.2 (No. 3) Ex. 2 4.18 50.0 5.63 4.12 69.8 6.01 5.76 1039.2 920.6 922.4 (No. 4) Ex. 2 4.18 47.9 5.66 4.13 58.4 6.23 5.86 1066.9 956.5 965.5 (No. 5) Average 4.17 48.7 5.67 4.12 61.2 6.15 5.85 1056.8 951.1 961.0 Com. 4.16 44.7 5.47 4.14 48.8 5.79 5.70 1085.6 1022.1 1019.6 Ex. 2 (No. 1) Com. 4.16 45.9 5.45 4.14 50.1 5.82 5.66 1082.9 1011.8 1009.3 Ex. 2 (No. 2) Average 4.16 45.3 5.46 4.14 49.5 5.81 5.68 1084.3 1017.0 1014.5

The measurements reported in Table 4 show that the battery cell prepared according to Example 2 and the battery cell prepared according to Comparative Example 2 perform similarly. As shown in Tables 3 and 4, the combination of succino nitrile and phenyl acetate maintains battery performance, improves battery stability at high temperatures, and ensures battery safety during overcharge.

The present invention has been described with reference to exemplary embodiments. However, those skilled in the art will appreciate that various modifications and substitutions can be made without departing from the spirit and scope of the present invention as set forth in the appended claims.

Claims

1. An electrolyte for a lithium battery comprising:

a non-aqueous organic solvent;
a lithium salt; and
a first additive capable of forming a chelating complex with a transition metal, the first additive being stable at voltages ranging from about 2.5 to about 4.8 V.

2. The electrolyte of claim 1, wherein the first additive comprises a compound selected from the group consisting of compounds represented by Formulas 1 to 3 and mixtures thereof:

wherein n is an integer ranging from 0 to 10,
n1 is an integer ranging from 0 to 15, wherein when n1 is an odd number, a is 1 and when n1 is an even number, a is either ½ or 1; and
at least one of R1 through R3 and at least one of R4 through R6 is a compound represented by AxR′, wherein A is selected from the group consisting of N, O, P, or S, x is 0 or 1, and R′ is selected from the group consisting of CN, C1 to C15 linear alkyls, C1 to C15 linear carboxyls, C1 to C15 branch alkyls and C1 to C15 branch carboxyls, and wherein the remaining R1 through R6 groups each comprises a material selected from the group consisting of H, halogens, C1 to C15 alkyls and C6 to C15 aryls.

3. The electrolyte of claim 2, wherein the first additive comprises a compound selected from the group consisting of compounds represented by Formulas 4 to 26:

4. The electrolyte of claim 1, wherein the first additive is present in the electrolyte in an amount ranging from about 0.1 wt % to about 10 wt % based on the total weight of electrolyte.

5. The electrolyte of claim 4, wherein the first additive is present in the electrolyte in an amount ranging from about 1 wt % to about 5 wt % based on the total weight of electrolyte.

6. The electrolyte of claim 4, wherein the first additive is present in the electrolyte in an amount ranging from about 3 wt % to about 5 wt % based on the total weight of electrolyte.

7. The electrolyte of claim 1, further comprising a second additive capable of releasing a transition metal from a positive electrode.

8. The electrolyte of claim 7, wherein the second additive is an ester-based compound.

9. The electrolyte of claim 8, wherein the second additive is selected from the group consisting of phenyl acetate, benzyl benzoate, ethyl acetate, 1-naphthyl acetate, 2-chromanone and ethyl propionate.

10. The electrolyte of claim 7, wherein the second additive is present in the electrolyte in an amount ranging from about 1 to about 10 parts by weight based on 100 parts by weight of the electrolyte.

11. The electrolyte of claim 10, wherein the second additive is present in the electrolyte in an amount ranging from about 1 to about 7 parts by weight based on 100 parts by weight of the electrolyte.

12. The electrolyte of claim 11, wherein the second additive is present in the electrolyte in an amount ranging from about 3 to about 5 parts by weight based on 100 parts by weight of the electrolyte.

13. The electrolyte claim 1, wherein the lithium salt is selected from the group consisting of LiPF6, LiBF4, LiSbF6, LiAsF6, LiClO4, LiCF3SO3, Li(CF3SO2)2N, LiC4F9SO3, LiAlO4, LiAlCl4, LiCl, Lil, LiN(CxF2x+1SO2)(CyF2y+1SO2) wherein x and y are natural numbers and mixtures thereof.

14. The electrolyte of claim 1, wherein the lithium salt has a concentration ranging from about 0.6 M to about 2.0 M.

15. The electrolyte of claim 1, wherein the lithium salt has a concentration ranging from about 0.7 M to about 1.6 M.

16. The electrolyte of claim 1, wherein the non-aqueous organic solvent is selected from the group consisting of carbonates, esters, ethers, ketones and mixtures thereof.

17. The electrolyte of claim 16, wherein the carbonates are selected from the group consisting of dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethylpropyl carbonate (EPC), methylethyl carbonate (MEC), ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC) and mixtures thereof.

18. The electrolyte of claim 16, wherein the esters are selected from the group consisting of n-methyl acetate, n-ethyl acetate, n-propyl acetate and mixtures thereof.

19. The electrolyte of claim 16, wherein the non-aqueous organic solvent comprises a carbonate comprising a mixture of chain carbonates and cyclic carbonates, the volume ratio of the chain carbonates to the cyclic carbonates ranging from about 1:1 to about 1:9.

20. The electrolyte of claim 1, wherein the non-aqueous solvent comprises a mixture of a carbonate solvent and an aromatic hydrocarbon solvent.

21. The electrolyte of claim 20, wherein the volume ratio of the carbonate solvent to the aromatic hydrocarbon solvent ranges from about 1:1 to about 30:1.

22. The electrolyte of claim 20, wherein the aromatic hydrocarbon solvent is selected from the group consisting of solvents represented by Formula 27:

wherein q is an integer ranging from 0 to 6 and R10 is selected from the group consisting of halogens and C1 to C10 alkyls.

23. The electrolyte of claim 22, wherein the aromatic hydrocarbon solvent is selected from the group consisting of benzene, fluorobenzene, toluene, trifluorotoluene, chlorobenzene, xylene and mixtures thereof.

24. The electrolyte of claim 1, further comprising a third additive selected from the group consisting of carbonates having halogen substituents, carbonates having cyano (CN) substituents, carbonates having nitro (NO2) substituents, vinylene carbonate, divinylsulfone, ethylene sulfite and mixtures thereof.

25. The electrolyte of claim 24, wherein the third additive is selected from the group consisting of carbonates having halogen substituents, carbonates having cyano (CN) substituents and carbonates having nitro (NO2) substituents.

26. The electrolyte of claim 24, wherein the third additive is selected from the group consisting of compounds represented by Formula 28:

wherein X1 is selected from the group consisting of halogens, cyano (CN) groups, and nitro (NO2) groups.

27. The electrolyte of claim 24, wherein the third additive is fluoroethylene carbonate.

28. An electrolyte for a lithium battery comprising:

a non-aqueous organic solvent;
a lithium salt;
a first additive capable of forming a chelating complex with a transition metal, the first additive being stable at a voltage ranging from about 2.5 to about 4.8 V;
a second additive capable of releasing a transition metal from a positive electrode.

29. The electrolyte of claim 28, further comprising a third additive selected from the group consisting of carbonates having halogen substituents, carbonates having cyano (CN) substituents, carbonates having nitro (NO2) substituents, vinylene carbonate, divinylsulfone, ethylene sulfite and mixtures thereof.

30. A lithium battery comprising:

an electrolyte comprising: a non-aqueous organic solvent, a lithium salt, and a first additive capable of forming a chelating complex with a transition metal, the first additive being stable at voltages ranging from about 2.5 to about 4.8 V;
a positive electrode comprising a positive active material capable of intercalating and deintercalating lithium ions; and
a negative electrode comprising an active material selected from the group consisting of materials capable of intercalating/deintercalating lithium ions, lithium metals, lithium-containing alloys, and materials capable of forming lithium-containing compounds by reversibly reacting lithium.

31. The lithium battery of claim 30, wherein the first additive comprises a compound selected from the group consisting of compounds represented by Formulas (1) to (3) and mixtures thereof:

wherein n is an integer ranging from 0 to 10,
n1 is an integer ranging from 0 to 15, wherein when n1 is an odd number, a is 1 and when n1 is an even number, a is either ½ or 1; and
at least one of R1 through R3 and at least one of R4 through R6 is a compound represented by AxR′, wherein A is selected from the group consisting of N, O, P, or S, x is 0 or 1, and R′ is selected from the group consisting of CN, C1 to C15 linear alkyls, C1 to C15 linear carboxyls, C1 to C15 branch alkyls and C1 to C15 branch carboxyls, and wherein the remaining R1 through R6 groups each comprises a material selected from the group consisting of H, halogens, C1 to C15 alkyls and C6 to C15 aryls.

32. The lithium battery of claim 31, wherein the first additive comprises a compound selected from the group consisting of compounds represented by Formulas 4 to 26 and mixtures thereof:

33. The lithium battery of claim 30, wherein the first additive is present in the electrolyte in an amount ranging from about 0.1 wt % to about 10 wt % based on the total weight of electrolyte.

34. The lithium battery of claim 33, wherein the first additive is present in the electrolyte in an amount ranging from about 1 wt % to about 5 wt % based on the total weight of electrolyte.

35. The lithium battery of claim 34, wherein the first additive is present in the electrolyte in an amount ranging from about 3 wt % to about 5 wt % based on the total weight of electrolyte.

36. The lithium battery of claim 30, wherein the electrolyte further comprises a second additive capable of releasing a transition metal from the positive electrode.

37. The lithium battery of claim 36, wherein the second additive is an ester-based compound.

38. The lithium battery of claim 37, wherein the second additive is selected from the group consisting of phenyl acetate, benzyl benzoate, ethyl acetate, 1-naphthyl acetate, 2-chromanone, and ethyl propionate.

39. The lithium battery of claim 36, wherein the second additive is present in the electrolyte in an amount ranging from about 1 to about 10 parts by weight based on 100 parts by weight of the electrolyte.

40. The lithium battery of claim 39, wherein the second additive is present in the electrolyte in an amount ranging from about 1 to about 7 parts by weight based on 100 parts by weight of the electrolyte.

41. The lithium battery of claim 40, wherein the second additive is present in the electrolyte in an amount ranging from about 3 to about 5 parts by weight based on 100 parts by weight of the electrolyte.

42. The lithium battery of claim 30, wherein the non-aqueous organic solvent is selected from the group consisting of carbonate, esters, ethers, ketones and mixtures thereof.

43. The lithium battery of claim 42, wherein the carbonates are selected from the group consisting of dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethylpropyl carbonate (EPC), methylethyl carbonate (MEC), ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC) and mixtures thereof.

44. The lithium battery of claim 30, wherein the non-aqueous solvent comprises a mixture of a carbonate solvent and an aromatic hydrocarbon solvent.

45. The lithium battery of claim 44, wherein the aromatic hydrocarbon solvent comprises a solvent represented by Formula 27:

wherein q is an integer ranging from 0 to 6 and R10 is selected from the group consisting of halogens and C1 to C10 alkyls.

46. The lithium battery of claim 45, wherein the aromatic hydrocarbon solvent is selected from the group consisting of benzene, fluorobenzene, toluene, trifluorotoluene, chlorobenzene, xylene and mixtures thereof.

47. The lithium battery of claim 30, wherein the electrolyte further comprises a third additive selected from the group consisting of carbonates having halogen substituents, carbonates having cyano (CN) substituents, carbonates having nitro (NO2) substituents, vinylene carbonate, divinylsulfone, ethylene sulfite and mixtures thereof.

48. The lithium battery of claim 47, wherein the third additive is selected from the group consisting of carbonates having halogen substituents, carbonates having cyano (CN) substituents and carbonates having nitro (NO2) substituents.

49. The lithium battery of claim 48, wherein the third additive is selected from the group consisting of compounds represented by Formula 28:

wherein X1 is selected from the group consisting of halogens, cyano (CN) groups, and nitro (NO2) groups.

50. The lithium battery of claim 48, wherein the negative active material comprises a carbonaceous material capable of intercalating/deintercalating lithium ions.

51. A lithium battery comprising:

a positive electrode comprising a positive active material capable of intercalating and deintercalating lithium ions;
a negative electrode comprising an active material selected from the group consisting of materials capable of intercalating/deintercalating lithium ions, lithium metals, lithium-containing alloys, and materials capable of forming lithium-containing compounds by reversibly reacting lithium; and
an electrolyte comprising: a non-aqueous organic solvent, a lithium salt, a first additive capable of forming a chelating complex with a transition metal, the first additive being stable at voltages ranging from about 2.5 to about 4.8 V, and a second additive capable of releasing a transition metal from the positive electrode.

52. The lithium battery of claim 51, wherein the electrolyte further comprises a third additive selected from the group consisting of carbonates having halogen substituents, carbonates having cyano (CN) substituents, carbonates having nitro (NO2) substituents, vinylene carbonate, divinylsulfone, ethylene sulfite and mixtures thereof.

Patent History
Publication number: 20060194118
Type: Application
Filed: Feb 28, 2006
Publication Date: Aug 31, 2006
Inventors: Kyoung-Han Yew (Suwon-si), Eui-Hwan Song (Suwon-si), Cheol-Soo Jung (Suwon-si), Yong-Beom Lee (Suwon-si)
Application Number: 11/365,299
Classifications
Current U.S. Class: 429/326.000; 429/330.000; 429/331.000; 429/332.000; 429/200.000
International Classification: H01M 10/40 (20060101);