# US 2013/0157147 A1 · Low Temperature Electrolyte for High Capacity Lithium Based Batteries > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2013/0157147 A1 - Document ID: US20130157147A1 - Status: Published application - Kind: A1 - Application number: 13/325,367 - Filed: 2011-12-14 - Published: 2013-06-20 - Earliest claimed: 2011-12-14 - Inventors: Bing Li; Shabab Amiruddin - Web page: https://patentgrep.com/patent/US20130157147A1 ## CPC - H01M 10/0569: characterised by the solvents - H01M 4/131: Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx - H01M 4/485: of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy (H01M4/505, H01M4/525 take precedence) - H01M 4/505: of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy - H01M 4/525: of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy - H01M 10/052: Li-accumulators - H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries - H01M 10/0567: characterised by the additives - H01M 10/0568: characterised by the solutes - H01M 4/133: Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx - H01M 2004/028: {Positive electrodes} - H01M 2220/20: Batteries in motive systems, e.g. vehicle, ship, plane - H01M 2300/0034: Fluorinated solvents - H01M 2300/004: Three solvents - Y02E 60/10: Energy storage using batteries - Y02T 10/70: Energy storage systems for electromobility, e.g. batteries - H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY - Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION - Y02T: CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION ## Abstract Electrolytes for lithium based batteries are described with good temperature tolerance over appropriate temperature ranges for uses in vehicles. In particular, the electrolytes are suitable for high voltage operation over 4.4V and can provide high rate performance. The electrolytes generally comprise a solvent that is a mixture of ethylene carbonate, dimethyl carbonate and ethylmethyl carbonate. Alternatively, a solvent combination of fluoroethylene carbonate and dimethyl carbonate was used. A primary lithium salt is includes at a concentration greater than about 1.05M. The electrolyte generally also comprises a lithium salt additive. The electrolytes can provide some battery capacity down to at least −40° C. while providing good performance also at elevated temperatures of 45° or more, and the corresponding batteries can be cycled to several thousand cycles. ## Claims ### Claim 1 An electrolyte for a lithium based battery comprising: from about 1.05M to about 2.0M LiPF6, LiBF4 or combinations thereof, a solvent consisting of ethylene carbonate, dimethyl carbonate and ethylmethyl carbonate with a weight ratio of ethylene carbonate to dimethyl carbonate of about 1:1 to about 1:4 and an ethylmethyl carbonate concentration of from about 5 weight percent to about 40 weight percent of the total weight of the electrolyte, and one or more lithium salt additives in a total amount from about 0.01 weight percent to about 10 weight percent of the total weight of the electrolyte. ### Claim 2 (depends on 1) The electrolyte of claim 1 wherein the LiPF6, LiBF4 or combinations has a concentration of about 1.05M to about 1.6M. ### Claim 3 (depends on 1) The electrolyte of claim 1 wherein the weight ratio of ethylene carbonate to dimethyl carbonate is from about 1:1.25 to 1:3 and the ethylmethyl carbonate concentration is from about 10 weight percent to about 30 weight percent of the total weight of the electrolyte. ### Claim 4 (depends on 1) The electrolyte of claim 1 wherein the lithium salt additive is represented by the formula: where b is the charge of the anion, m is a number from 1 to 4, n is a number from 1 to 8, q is 0 or 1, M is a transition metal or an element selected from groups 13-15 of the periodic table, R1 is an organic group, R2 is a halogen or an organic group, X1 and X2 are independently O, S or NR4, and R4 is a halogen or an organic group. ### Claim 5 (depends on 1) The electrolyte of claim 1 wherein the lithium salt additive comprises lithium difluoro oxalato borate (LiDFOB), lithium bis(oxalato)borate (LiBOB), lithium fluorododecaborate (Li2B12HxF12-x(x=0−3)), lithium (bis)trifluoromethane sulfonimide, or a combination thereof. ### Claim 6 (depends on 1) The electrolyte of claim 1 further comprising one or more non-ionic organic additives in a total amount of no more than about 30 weight percent of the total weight of the electrolyte. ### Claim 7 (depends on 6) The electrolyte of claim 6 wherein the non-ionic organic additive is selected from the group consisting of N,N-diethylamino trimethylsilane, 2,5-dihydrofuran, ethylmethyl sulfone, fluoroethylene carbonate, gamma-butyrolactone, monomer of polyethylene oxide, monomer of polyvinylidine fluoride, and mixtures thereof. ### Claim 8 (depends on 6) The electrolyte of claim 6 wherein the non-ionic organic additive is fluoroethylene carbonate. ### Claim 9 (depends on 1) A lithium based battery, comprising: a positive electrode comprising a lithium intercalation material, a negative electrode, a separator between the negative electrode and the positive electrode, and an electrolyte of claim 1. ### Claim 10 (depends on 9) The battery of claim 9 wherein the battery has a discharge capacity at −30 degrees Celsius that is at least about 40% of the room temperature discharge capacity. ### Claim 11 (depends on 9) The battery of claim 9 wherein the battery has a discharge capacity at −40 degrees Celsius that is at least about 25% of the room temperature discharge capacity. ### Claim 12 (depends on 9) The battery of claim 9 wherein the battery maintains at least 60% discharge capacity at 45 degree Celsius after cycling for 1500 cycles when discharged from 4.35V to 2.2V at 1C. ### Claim 13 A lithium based battery, comprising: a positive electrode comprising a lithium intercalation material, a negative electrode, a separator between the negative electrode and the positive electrode, and an electrolyte comprising LiPF6 and/or LiBF4, a solvent consisting of ethylene carbonate, dimethyl carbonate and ethylmethyl carbonate, and one or more lithium salt additives, wherein the battery has a specific capacity of at least about 80 mAh/g relative to the weight of the positive electrode active material when discharged at −30° C. from 4.5V to 2 V at a rate of C/10. ### Claim 14 (depends on 13) The battery of claim 13 wherein the positive electrode comprises a lithium metal oxide approximately represented by the formula Li1+bNiαMnβCoγAδO2-zFz, where b ranges from about 0.01 to about 0.3, a ranges from about 0 to about 0.4, β range from about 0.2 to about 0.65, γ ranges from 0 to about 0.46, δ ranges from 0 to about 0.15 and z ranges from 0 to about 0.2 with the proviso that both a and y are not zero, and where A is Mg, Sr, Ba, Cd, Zn, Al, Ga, B, Zr, Ti, Ca, Ce, Y, Nb, Cr, Fe, V, Li or combinations thereof. ### Claim 15 (depends on 13) The battery of claim 13 wherein the negative electrode comprises a lithium intercalation/alloying material. ### Claim 16 (depends on 13) The battery of claim 13 wherein the negative electrode comprises graphitic carbon, silicon based material, or a combination thereof. ### Claim 17 (depends on 13) The battery of claim 13 wherein the negative electrode comprises lithium foil, lithium metal, lithium metal alloy, or a combination thereof. ### Claim 18 (depends on 13) The battery of claim 13 wherein the LiPF6, LiBF4 or combination thereof has a concentration from about 1.05M to about 2.0M. ### Claim 19 (depends on 13) The battery of claim 13 wherein the weight ratio of ethylene carbonate to dimethyl carbonate is about 1:1.25 to 1:3 and the ethylmethyl carbonate concentration is about 10 weight percent to about 30 weight percent of the total weight of the electrolyte. ### Claim 20 (depends on 13) The battery of claim 13 wherein the total amount of one or more lithium salt additives is about 0.01 weight percent to about 10 weight percent of the total weight of the electrolyte. ### Claim 21 (depends on 13) The battery of claim 13 wherein the lithium salt additive comprises lithium difluoro oxalato borate (LiDFOB), lithium bis(oxalato)borate (LiBOB), lithium fluorododecaborate (Li2B12HxF12-x(x=0−3)), lithium (bis)trifluoromethane sulfonimide, or a combination thereof. ### Claim 22 (depends on 13) The battery of claim 13 further comprising one or more non-ionic organic additives in a total amount of no more than about 30 weight percent of the total weight of the electrolyte. ### Claim 23 (depends on 22) The battery of claim 22 wherein the non-ionic organic additive is fluoroethylene carbonate. ### Claim 24 (depends on 13) The battery of claim 13 wherein the battery has a discharge capacity at −30 degrees Celsius that is at least about 40% of the discharge capacity at room temperature. ### Claim 25 (depends on 13) The battery of claim 13 wherein the battery has a discharge capacity at −40 degrees Celsius that is at least about 25% discharge capacity at room temperature. ### Claim 26 A lithium based battery comprising: a positive electrode comprising a lithium metal oxide approximately represented by the formula Li1+bNiαMnβCoγAδO2-zFz, where b ranges from about 0.01 to about 0.3, α ranges from about 0 to about 0.4, β range from about 0.2 to about 0.65, γ ranges from 0 to about 0.46, δ ranges from 0 to about 0.15 and z ranges from 0 to about 0.2 with the proviso that both α and γ are not zero, and where A is Mg, Sr, Ba, Cd, Zn, Al, Ga, B, Zr, Ti, Ca, Ce, Y, Nb, Cr, Fe, V, Li or combinations thereof. a negative electrode, a separator between the negative electrode and the positive electrode, and an electrolyte comprising from about 1.05M to about 2.0M of LiPF6 and/or LiBF4, and a solvent consisting of ethylene carbonate, dimethylcarbonate and ethylmethyl carbonate with a weight ratio of ethylene carbonate to dimethyl carbonate of 1:1 to 1:4 and ethylmethyl carbonate concentration is from about 5 weight percent to about 40 weight percent of the total weight of the electrolyte. ### Claim 27 (depends on 26) The battery of claim 26 wherein the lithium metal oxide can be approximately represented by a formula of xLi2M′O3.(1−x) LiMO2, where M′ represents one or more metal ions having an average valance of +4 and M represents one or more metal ions having an average valance of +3, and 0.03