Patent Application
20100167121
The present invention relates to a nonaqueous electrolyte. The nonaqueous electrolyte of the present invention can be used most appropriately in a lithium secondary cell.
Primary cells and secondary cells contain one or multiple electrochemical cells. Many cells contain lithium because of the high reduction potential of lithium, low molecular weight of elemental lithium, and high output density. The small size and high mobility of lithium cations make possible rapid recharging in secondary cells. These advantages make lithium secondary cells ideal for portable telephones, laptop computers, and other such portable electronic devices. Larger lithium cells are also being developed recently for use in the hybrid electric automobile market.
Lithium secondary cells are superior to existing primary and secondary cell technology because of the high reduction potential and low molecular weight of elemental lithium and dramatically improve the output density. A lithium secondary cell is a cell that contains metallic lithium as the cathode. There are also cells that contain a lithium ion host material as the cathode known as lithium ion cells. A secondary cell is a cell intended to undergo multiple cycles of charging and discharging. The small size and high mobility of the lithium cation enables rapid recharging. These advantages make lithium secondary cells ideal for portable telephones, laptop computers, and other such portable electronic devices. Larger lithium ion cells are also recently being developed and are intended for use in the hybrid car market.
The main problem encountered in the reversibility of cell charging and discharging was the reactivity of these to the electrolyte components (salts and solvents) under varying conditions. It was observed in the past that all of the electrolyte salts and solvents are reduced to some extent at the cathode during the initial charging step. This reduction forms a conductive inactivated layer or a film called a solid electrolyte interphase, that is, SEI, layer. Reduction, however, continues with the charging/discharging cycle, and the reversible capacity at the cathode can finally be lost.
A particular problem in the above-mentioned use in hybrid electric automobiles has been making the life of the lithium ion cell as long as possible. Suppressing “undesirable” reactions in the cell was important to this end.
As was mentioned above, the life tended to shorten with repeated charging/discharging cycles in conventional lithium ion cells.
Examples of conventional batteries are described in US Patent Pub No 2007/0048605 A1 (hereby incorporated by reference and corresponding to JP Kokai 2007-87938) and JP Kokai 2006-202745.
The object of the present invention is to resolve the above-mentioned drawbacks of the prior art and to provide a nonaqueous electrolyte that makes it possible to lengthen the life of a lithium ion cell when used in a lithium ion cell even when subjected to repeated charging/discharging cycles.
Another object of the present invention is to provide a lithium ion cell that can achieve a longer life even when subjected to repeated charging/discharging cycles.
As a result of in-depth research, the present inventors discovered that combining two types of additives having specific structures with a lithium salt having a specific structure is very effective for attaining the above goals.
The nonaqueous electrolyte of the present invention is based on the above knowledge. More specifically, it is characterized by containing a nonaqueous solvent,
a lithium salt shown by the following formula (1)
Li2B12HxF12−x (1)
(where, x is an integer of from 0 to 3),
at least one first additive among compounds shown by the following formula (2)
(where, X and Y are independently H, CH3, a vinyl group, or F),
(where, X and Y are independently H, CH3, a vinyl group, or F),
and at least one second additive among compounds shown by the following formula (3)
(where, Y is O, X is H or OH, and n is an integer of 0-5).
As was mentioned above, the present invention provides a nonaqueous electrolyte that makes it possible to lengthen the life of a lithium ion cell when used in a lithium ion cell even when subjected to repeated charging/discharging cycles.
The present invention also provides a lithium ion cell that makes it possible to actualize longer life even when subjected to repeated charging/discharging cycles.
The present invention also provides a lithium ion cell capable of maintaining higher discharge capacity even when subjected to repeated charging/discharging cycles.
The present invention will be explained more concretely below, referring to the drawings as needed. The terms “parts” and “%” that express the ratios below are based on weight unless specifically stated otherwise (however, solvent compositions are based on “volume” unless specifically stated otherwise).
The electrolyte of the present invention contains at least a nonaqueous solvent, a lithium salt having a specific structure, and two types of additives having specific structures.
As lithium salts that can be used in the present invention, examples of the lithium salt that constitutes the electrolyte salt of the present invention are lithium fluoroborates shown by the following formula (1)
Li2B12HxF12−x (1 )
(where, x is an integer of from 0 to 3)
(Examples of Preferred Lithium Salts)
More specifically, compounds in which x=0 are preferred among compounds shown by the above formula (1) for their high oxidation resistance (that is, long life).
The first additive in the present invention is at least one additive among compounds shown by the following formula (2):
(where, X and Y are independently H, CH3, a vinyl group, or F)
The following compounds among the above-mentioned first additives are especially suitable for use from the standpoint of cell performance.
For example, at least one additive selected from vinylene carbonate (VC), vinyl ethylene carbonate (VEC), dimethyl vinylene carbonate (DMVC), and fluorinated ethylene carbonate (FEC).
VC among these is especially preferred from the standpoint of not raising the internal resistance.
The second additive in the present invention is at least one additive among compounds shown by the following formula (3):
(where, Y is O, X is H or OH, and n is an integer of 0-5).
The following compounds among the above-mentioned second additives are especially suitable for use from the standpoint of their stability at high temperature.
For example, at least one additive selected from propane sultone (PS) and hydroxypropane sultone (HOPS).
PS among them is especially preferred for its good ability to suppress gas production.
The following can be given as examples of suitable combinations of first and second additives in the present invention from the standpoint of the balance of cell performance and life.
The following can be given as examples of suitable combinations of lithium salt, first and second additives in the present invention from the standpoint of the balance of cell performance and life.
The nonaqueous solvent (also sometimes referred to as the “carrier”) that can be used in the present invention is not particularly restricted.
Examples of the aprotic solvent or carrier that forms the electrolyte include at least one member selected from the group consisting of ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), methyl propyl carbonate (MPC), ethyl propyl carbonate (EPC), dipropyl carbonate (DPC), bis(trifluoroethyl)carbonate, bis(pentafluoropropyl)carbonate, trifluoroethyl methyl carbonate, pentafluoroethyl methyl carbonate, heptafluoropropyl methyl carbonate, perfluorobutyl methyl carbonate, trifluoroethyl ethyl carbonate, pentafluoroethyl ethyl carbonate, heptafluoropropyl ethyl carbonate, perfluorobutyl ethyl carbonate, and the like, fluorinated oligomers, dimethoxyethane, triglyme, tetraethylene glycol, dimethyl ether (DME), polyethylene glycol, sulfone, and γ-butyrolactone (GBL). The solvent or carrier may contain at least one type of ionic liquid. The term ionic liquid also refers to any type of room-temperature molten salt [sic]. Examples of suitable ionic liquids include in particular at least one member selected from asymmetrical tetraalkyl ammonium salts of weakly coordinated anions that do not contain active hydrogen or reducible hydrogen in the liquid cation, for example, butyl trimethylammonium tetrafluoroborate, hexyl trimethylammonium trifluoromethanesulfonimide, and the like, and N-alkyl piperidium [sic; piperidinium] salts of weakly coordinated anions, for example, N-methylpiperidinium tetrafluoroborate, N-ethylpiperidinium trifluoromethanesulfonate, and N-butylpiperidinium trifluoromethanesulfonimide.
The following can be given as examples of suitable combinations of nonaqueous solvent, lithium salt, first and second additives in the present invention from the standpoint of the balance of cell performance and life (the composition ratios are volume ratios (parts)).
EC/PC=30/5 and DMC/EMC/DEC=65/10/40 (1)
EC/PC=30/10 and DMC/GBC=40/20 (2)
or EC/PC=30/10 and EMC/GBC=40/20
or EC/PC=30/10 and DEC/GBC=40/20
PC/EC=(5−20)/(20−4) and (DMC or EMC or DEC)/GBC=(20−65)/(5−25) (3)
Taking the capacity after 100 charge/discharge cycles as Cap (100) and the capacity after 200 charge/discharge cycles as Cap (200), the ratio thereof R (Cap)=Cap (200)/Cap (100) of a lithium ion cell that employs the nonaqueous electrolyte of the present invention is preferably or more. This ratio R (Cap) is more preferably [blank space] or more (ideally [blank space] or more).
The values of the above-mentioned Cap (100) and/or Cap (200) can be determined by “interpolation” by the following formula from the capacity after the before and after charge/discharge cycles (for example, the capacity of (100−a) times and (100+b) times; (200−c) times and (200+d) times [translator's note: no closing parenthesis].
The values of the above-mentioned Cap (100) and Cap (200) can be measured appropriately by using the conditions discussed below in Working Example 1.
In another embodiment, the electrolyte of the present invention may include an aprotic gel polymer carrier/solvent. A suitable gel polymer carrier/solvent may include at least one member selected from the group consisting in particular of polyethers, polyethylene oxides, polyimides, polyphosphazines, polyacrylonitriles, polysiloxanes, polyether grafted polysiloxanes, derivatives of the above, copolymers of the above, crosslinked and network structures of the above, and blends of the above. A suitable ionic electrolyte salt is added. Other gel polymer carriers/solvents may include those prepared from a polymer matrix derived from at least one member selected from the group consisting of polypropylene oxides, polysiloxanes, sulfonated polyimides, perfluorinated membranes (Nafion™ resins), divinyl polyethylene glycols, polyethylene glycol-bis(methylacrylates), polyethylene glycol-bis(methyl methacrylates), derivatives of the above, copolymers of the above, and crosslinked and network structures of the above. The aprotic gel polymer carrier may contain any of the aprotic liquid carriers listed above.
When the electrolyte contains an electrolyte in a solution [sic], the salt concentration is typically from about 0.05 to about 2 mol, or from about 0.1 to about 1.2 mol or from about 0.2 to about 0.5 mol. The viscosity tends to become overly high when the concentration is raised, and the bulk conductivity characteristics of the cell that utilizes the electrolyte are sometimes negatively affected.
The cell of the present invention contains a cathode, anode, and the electrolyte of the present invention. In certain embodiments, the anode and cathode of the cell may be any type of lithium-containing substance being utilized or a substance such as lithium and the like that can “host” an ion in reduced form or oxidized form. The term “host” means a substance capable of reversibly segregating an ion, for example, a lithium ion. The cathode of the cell of the present invention may include at least one member selected from the group consisting of metallic lithium, a carbonaceous substance, for example, amorphous carbon or graphite (natural or manmade), tin and alloys thereof, silicon and alloys thereof, germanium and alloys thereof, metal oxides, and derivatives of these substances (for example, lithium titanate).
The anode used in the cell of the present invention in particular may be based on a lithium composite oxide that combines cobalt, nickel, manganese, a mixture of these, or other such transition metals or a lithium composite oxide in which some of the lithium sites or transition metal sites are substituted by at least one member selected from the group consisting of cobalt, nickel, manganese, aluminum boron, magnesium, iron, copper, and the like. Examples of such lithium composite oxides include compounds having the formula LiMOx (where, M is a metal; M=Cu, Mn, Ni . . . Mn+Ni, and the like). Other examples include what are called “olivine type” phosphate compounds having a formula LiMPO4 (where, M is a metal; M=Fe, Mn, Co, Ni . . . and the like).
Concrete examples of the lithium composite used as the anode include lithium iron phosphates, LiFePO4, LiNi1−xCOxO2, and lithium manganese spinel, LiMn2O4.
The separator of the lithium cell in the present invention may include a microporous polymer film. Examples of the polymer that forms the film in particular include at least one member selected from the group consisting of nylon, cellulose, nitrocellulose, polysulfone, polyacrylonitrile, polyvinylidene fluoride, polypropylene, polyethylene, polybutene, and mixtures thereof. A ceramic separator, particularly one based on a silicate, aluminosilicate, and derivatives of these, can also be used. The electrolyte wetting of the separator can be improved by adding a surfactant to the separator or electrolyte. Other components or compounds known to be used in electrolytes or cells may also be added.
In certain embodiments, the cell is constructed from a carbonaceous lithium ion-hosting cathode, anode, separator, and a lithium-based electrolyte salt carried in an aprotic solvent, gel polymer, or polymer matrix. Examples of the carbonaceous cathode are graphite and hard carbon.
Various embodiments of the present invention are explained in the examples below; these in no way limit the scope of the claims attached to this application.
The present invention is explained more concretely below through working examples.
[Preparation of Li2B12HxF12−x (x=0-3)]
A colorless slurry containing 2.96 g (11.8 mmol) of K2B12H12CH3OH in 6 mL of formic acid at an average Hammett acidity of H0=−2 to −4 was fluorinated at 0-20° C. 100% of the desired F2 (142 mmol) was added as a mixed gas of 10% F2/10% O2/80% N2, and a colorless solution remained. A solid precipitated from the solution through further fluorination (3%) at 30° C. A quantity of 5.1 g of a colorless, brittle solid was obtained by evacuating the solvent overnight. This crude product was analyzed by 19F NMR and was found to be mainly B12F10H22− (60%), B12F11H2− (35%), and B12F122− (5%). The crude product was dissolved in water, and the pH of the solution was adjusted to 4-6 using triethylamine and triethylamine hydrochloride. The precipitated product was filtered out, dried, and again suspended in water. Two equivalents of lithium hydroxide monohydrate was added to this slurry, and the resulting triethylamine was evacuated. After distilling off all of the triethylamine, more lithium hydroxide was added, and the pH of the final solution was brought to 9-10. The water was removed by distillation, and the final product was vacuum dried for 4-8 hours at 200° C. The typical yield of Li2B12FxH12−x (x=10, 11, 12) was about 75%.
[Preparation of Li2B12FxH12−x (x=10−12)]
A colorless slurry containing 2.96 g (11.8 mmol) K2B12H12CH3OH in 6 mL formic acid at an average Hammett acidity of H0=−2 to −4 was fluorinated at 0 to 20° C. 100% of the desired F2 (142 mmol) was added as a mixture of 10% F2/10% O2/80% N2, and a colorless solution remained. A solid precipitated from the solution through further fluorination (3%) at 30° C. A quantity of 5.1 g of a colorless, brittle solid was obtained by evacuating the solvent overnight. This crude product was analyzed by 19F NMR and was found to be mainly B12F10H22− (60%), B12F11H2− (35%), and B12 F122− (5%). The crude product was dissolved in water, and the pH of the solution adjusted to 4-6 using triethylamine and triethylamine hydrochloride. The precipitated product was filtered, dried, and again suspended in water. Two equivalents of lithium hydroxide monohydrate was added to this slurry, and the resulting triethylamine was evacuated. After distilling off all of the triethylamine, more lithium hydroxide was added, and the pH of the final solution was brought to 9-10. The water was removed by distillation, and the final product was vacuum dried for 4-8 hours at 200° C. The typical yield of Li2B12FxH12−x (x=10, 11, 12) was about 75%.
[Preparation of Li2B12FxBr12−x (x≧10, average x=11)]
A quantity of 3 g (0.008 mol) of Li2B12FxH12−x (x≧10) of an average composition of Li2B12F11H was dissolved in 160 mL of 1 M HCl (aq). A quantity of 1.4 mL (0.027 mol) of Br2 was added, and this mixture was refluxed for four hours at 100° C. A sample was taken for NMR analysis.
Part of the above sample was returned to reflux, and chlorine was added over six hours to form a stronger brominating agent BrCl. An aliquot as taken when chlorine addition was completed, and NMR analysis showed the composition of this aliquot to be the same as that of the starting aliquot. The HCl and water were distilled off, and the product was vacuum dried at 150° C. A total of 2.55 g of a white, solid product was isolated. The theoretical amount of Li2B12FxBr12−x (x≧10, average x=11) was 3.66 g.
[Refining of Li2B12F12 from sodium and potassium] [sic]
An aqueous solution of Li2B12F12 containing approximately 200 ppm of sodium was eluted through column having an Li+ form cation exchange resin DOWEX 50WX8-200. The water was distilled off from the eluate, and the residue was vacuum dried at 150° C. The refined salt Li2B12F12 contained about 60 ppm of sodium when measured by ICP.
[Thermogravimetric analysis (TGA)/IR of Li2B12F12]
TGA/IR analysis was performed by ramping the sample in TA 2960 SDT and heating from room temperature to 800° C. at 10° C./min in 100 cc/min of N2, H2O, saturated N2, or air. The gas released was passed through a 10 cm IR gas cell. The IR spectrum was collected at a resolution of 4 cm−1 and a gain of 1 by AVATAR IR. The spectrum was collected as a series of spectra at 1-minute intervals. The profile of the released gas was created by measuring the absorbance related to various compounds at the band maximum in the IR spectrum. Quantitative information was derived by multiplying the area under the profile curve by the calibration factor and dividing by the sample weight. The IR profile shown in
Approximately 200 g of Li2B12F12 salt prepared according to Production Example 2 was ground and dried for 8 hours at 250° C. under a 30 mTorr dynamic vacuum. The sample was transferred to a drying box having an argon-filled inert atmosphere. Moisture analysis of this salt was carried out by an Orion AF7 coulometric Karl Fischer titrator. Hydranal™ Karl Fischer reagent and standards made by Riedel-deHaen were used. Approximately 0.60 g of Li2B12F12 was dissolved in 3 mL of acetonitrile, and from 3 to 1 mL was taken for water analysis. After this drying procedure, a water value of about 100 ppm was obtained on a salt weight basis. Vacuum drying in this method typically gave water readings of 100-500 ppm.
Approximately 100 g of Li2B12F12 salt prepared according to Production Example 2 was ground and dried for four hours at 150-200° C. under a 100 mTorr dynamic vacuum. The sample was further ground and loaded onto a quartz frit in a vertical glass tube. This tube was externally heated to 260° C., and dry nitrogen was purged through the salt at a rate sufficient to fluidize the salt bed. After 12 hours, the sample was cooled and transferred to a box having an argon-filled inert atmosphere for analysis of the water content. Karl Fischer analysis, performed in the same way as in Example 7, showed the salt to contain 10-20 ppm of water on a salt weight basis.
Li2B12F12 (purity 99.5% or more), a lithium salt, was stored in an argon glove box kept at a dew point of −80° C. or lower and supplied for preparation of the electrolyte after fluorinating the raw material according to Production Example 2, removing the impurities, and drying.
The purity of the Li2B12F12 obtained assessed by liquid chromatography (LC) was 99.5%. The water content assessed by the Karl Fischer (KF) method was 20 ppm. The solvent used in the electrolyte was refined to a water content of 10 ppm or less.
A quantity of 14.96 g of Li2B12F12 salt was weighed out as the electrolyte 1 of Working Example 1, and 100 mL of solution was prepared by dissolving the electrolyte in a mixed solvent of PC:EC:DEC=5:30:65 vol % (where, PC: propylene carbonate, EC: ethylene carbonate, DEC: diethyl carbonate) that contained 2 wt % vinylene carbonate (VC) and 1 wt % propane sultone (PS) to prepare an electrolyte 1 of 0.4 mol/L of Li2B12F12 salt.
The conductivity of this electrolyte 1 measured at 1 kHz was 4.75 mS/cm, and the viscosity was 6.8 cP.
Next, a laminated cell was prepared by the following procedure to assess the cell characteristics. First, a mixture of 80 wt % LiMn2O4 and 20 wt % LiNi0.8Co0.18Al0.02O2 was taken as the anode active substance A, and an anode paste was prepared by dissolving this and a mixture B of 10 wt % acetylene black and 90 wt % graphite as a conductive material and polyvinylidene fluoride C as a binder in N-mertipyrrolidone [sic] (NMP) to make a dry weight ratio of A:B:C=85:8:7 wt %. The paste was applied to an anode current collector 1 made of aluminum foil, dried, and pressed to prepare an anode electrode having a anode layer 2 formed on both surfaces of the anode current collector 1. A cathode paste was prepared by dissolving manmade graphite D and C in NMP to make D:C=92:8 wt % by dry weight. The paste was applied to a cathode current collector 3 made of copper foil, dried, and pressed to prepare a cathode electrode having a cathode layer 4 formed on both surfaces of the cathode current collector 3.
Sixteen cathodes and 15 anodes were alternately laminated via separators 5 with the tab terminal parts of the electrodes prepared facing the opposite directions. An anode terminal 6 made of aluminum for the anodes and a cathode terminal 7 made of nickel for the cathodes were connected by ultrasonic welding to the tab terminals of the anodes and cathodes. [The construct was] inserted in a casing made of an aluminum laminate sheet, and the base and edges of the anode and cathode terminals were sealed by heat sealing. The electrolyte 1 prepared above was introduced from the top. After vacuum degassing, the top was temporarily sealed by heat sealing, and a laminated cell A having a planned capacity of about 4 Ah for cell assessment was produced (
The cell 1 prepared was allowed to stand for 8 hours after filling until the electrolyte had conditioned the electrode. It was then charged to 3.2 V at 0.1 C (400 mA), and allowed to stand for another 8 hours. Next, it was charged to 4.2 V at 0.2 C (800 mA) and charged at a constant voltage until the current value reached 40 mA by 4.2 V. After standing for another 8 hours in this state, it was discharged at a constant current to 2.7 V at 0.2 C. After measuring the discharge capacity, the top seal was cut away, the gas was removed, and the top was again sealed by heat sealing. The starting discharge capacity of the laminated cell 1 was 3.97 Ah. Next, to evaluate the life of this cell, the cell 1 was charged for 3.5 h by a constant current-constant voltage of 4.2 V at 0.5 C and stored in this state in a 60° C. constant temperature tank. After a certain period of time, the stored cell was removed from the constant temperature tank and the residual capacity at 0.2 C and, after charging at 0.5 C, the recovered discharge capacity at 0.2 C were assessed at 25° C. Such testing was conducted by varying the voltage during storage between 3.95 V and 4.1 V, and the graph of the changes in capacity shown in
The test conditions in
SOC 100% cycle test
Charging: Current value 1 C (4 A), 4.2 V, CC-CV (constant current-constant voltage)
3.5 hr cut
Discharging: Current value 1 C (4 A), 2.7 V cut
The graph of
The test conditions in
Storage voltage: 4.2, 4.1, 3.9 V
Studies were conducted in the same way as in Working Example 1 except that the conditions were varied as shown in the graphs in
(Effects of the Dielectric Constant of the Solvent on 1,2-dimethoxy-4-bromobenzene as an Overcharge Protection Additive)
U.S. Pat. No. 5,763,119 (hereby incorporated by reference) disclosed the use of 1,2-dimethoxy-4-bromobenzene as an overcharge protection redox shuttle. 0.1 M 4-bromo-1,2-dimethoxybenzene was added to 1.0 M LiPF6 in EC:DEC (3:7) (dielectric constant=28) solution and 1.0 M LiPF6 in PC solution (dielectric constant up to 65). A cyclic voltammetry test was conducted in an electrochemical cell that was the same as the one described in Examples 2-6. The scan speed was 20 mV/sec. The oxidation threshold potential in the solvents containing EC/DEC and PC was 4 and 18 V. The dielectric constant of the solvent had no effect on the oxidation threshold potential.
In the results, the cell was not overcharged up to a set voltage of 5.5 volt and a flat plateau was observed at about 4.6 volt due to oxidation of the overcharge protection salt when 0.2 M Li2B12F12 in an LiPF6 electrolyte was used. Through this cell design, the use of Li2B12F12 salt in a lithium secondary cell having LiPF6 salt gives overcharge protection, and a sufficient amount was present to create a redox shuttle during overcharge conditions.
The results obtained are shown in the graph of
25° C. Overcharge test
SOC Overcharge from 100% (4.2 V)
Current value 1 C (4 A)
In the graph, curve 1 shows the voltage of Working Example 1.
Curve 1′ shows the surface temperature of Working Example 1.
Curve 2 shows the voltage of the comparative example.
Curve 2′ shows the surface temperature of the comparative example.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2008-335160 | Dec 2008 | JP | national |
