CA3071314A1 - Novel battery systems based on lithium difluorophosphate utiling methyl acetate, carbonate solvent and lithium nickel manganese cobalt oxid - Google Patents
Novel battery systems based on lithium difluorophosphate utiling methyl acetate, carbonate solvent and lithium nickel manganese cobalt oxid Download PDFInfo
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- CA3071314A1 CA3071314A1 CA3071314A CA3071314A CA3071314A1 CA 3071314 A1 CA3071314 A1 CA 3071314A1 CA 3071314 A CA3071314 A CA 3071314A CA 3071314 A CA3071314 A CA 3071314A CA 3071314 A1 CA3071314 A1 CA 3071314A1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0569—Liquid materials characterised by the solvents
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/10—Batteries in stationary systems, e.g. emergency power source in plant
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0037—Mixture of solvents
- H01M2300/004—Three solvents
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Description
BACKGROUND
TECHNICAL FIELD
[0001] The present disclosure relates to rechargeable battery systems, and more specifically to the chemistry of such systems, including operative electrolyte additives and electrodes for improving the properties of the rechargeable lithium-ion-battery systems.
DESCRIPTION OF RELATED ART
2017/0025706 at Tables 1 and 2.)U520170025706 discloses that a third compound, often tris(-trimethly-sily1)-phosphate (TTSP) or tris(-trimethyl-sily1)-phosphite (TTSPi), was necessary in concentrations of between 0.25-3 wt% to produce a robust lithium-ion-battery system. (See, e.g., U.S. 2017/0025706 at 72.) However, because additives can be expensive and difficult to include within Li-ion batteries on a manufacture scale, simpler, yet effective battery systems are needed, including those with fewer additives.
SUMMARY
When used as part of a greater battery system (which includes the electrolyte, electrolyte solvent, positive electrode, and negative electrode), these two-operative, additive electrolyte systems produce desirable properties for energy storage applications, including in vehicle and grid applications.
The positive electrode may be coated with a material such as aluminum oxide (A1203), titanium dioxide (TiO2), or another coating. Further, as a cost savings, the negative electrode may be formed from natural graphite, however depending on the pricing structure, in certain instances artificial graphite is cheaper than natural graphite.
Exemplary battery systems include two additives (for example, FEC, VC, or PES and DTD or another sulfur-based additive), a graphite negative electrode (either naturally occurring graphite or an artificial, synthetic graphite), an NMC positive electrode, a lithium electrolyte (formed from, for example, a lithium salt such as lithium hexafluorophosphate with chemical composition LiPF6), and an organic or non-aqueous solvent. A lithium-ion battery may include a negative electrode, a positive electrode comprising NMC with micrometer-scale grains, and a nonaqueous electrolyte comprising lithium ions dissolved in a first nonaqueous solvent, and an additive mixture having a first operative additive of either fluoro ethylene carbonate or vinylene carbonate and a second operative additive of either 1,3,2-dioxathiolane-2,2-dioxide, another sulfur-containing additive, or lithium difluorophosphate.
BRIEF DESCRIPTION OF THE DRAWINGS
DTD.
DTD.
DTD.
DTD, 2% FEC, and 2% FEC + 1% DTD.
FEC + 1% MMDS, cycling between 3.0 V and 4.3 V at 40 C in a base electrolyte of 1.2M
LiPF6 in 30% ethylene carbonate and 70% ethyl methyl carbonate.
FEC + 1% MMDS, cycling between 3.0 V and 4.3 V at 40 C in a base electrolyte of 1.2M
LiPF6 in 30% ethylene carbonate and 70% ethyl methyl carbonate.
FEC, 1% FEC +
1% DTD, 2% FEC + 1% DTD, 1% FEC + 1% MMDS, and 2% FEC + 1% MMDS, cycling between 3.0 V and 4.3 V at 40 C in abase electrolyte of 1.2M LiPF6 in 30%
ethylene carbonate and 70% ethyl methyl carbonate.
+ 1% MMDS, cycling between 3.0 V and 4.3 V at 40 C in a base electrolyte of 1.2M LiPF6 in 30% ethylene carbonate and 70% ethyl methyl carbonate.
+ 1% MMDS, cycling between 3.0 V and 4.3 V at 40 C in a base electrolyte of 1.2M LiPF6 in 30% ethylene carbonate and 70% ethyl methyl carbonate.
FEC, 1% VC +
1% DTD, 2% VC + 1% DTD, 1% VC + 1% MMDS, and 2% VC + 1% MMDS, cycling between 3.0 V and 4.3 V at 40 C in abase electrolyte of 1.2M LiPF6 in 30%
ethylene carbonate and 70% ethyl methyl carbonate by weight.
PES + 1% MMDS, cycling between 3.0 V and 4.3 V at 40 C in a base electrolyte of 1.2M
LiPF6 in 30% ethylene carbonate and 70% ethyl methyl carbonate.
FEC, 1% PES +
1% DTD, 2% PES + 1% DTD, 1% PES + 1% MMDS, and 2% PES + 1% MMDS, cycling between 3.0 V and 4.3 V at 40 C in abase electrolyte of 1.2M LiPF6 in 30%
ethylene carbonate and 70% ethyl methyl carbonate.
FEC + 0% MA as a function of the voltage for different electrolyte compositions that contain FEC in the voltage range of 4.0 V to 4.2 V.
FEC + 0% MA as a function of the voltage for different electrolyte compositions that contain FEC in the voltage range of 4.0 V to 4.3 V. FIG 12 A shows results for the first cycle to 4.3 V.
Figure 12B shows results for the second cycle.
FEC + 0% MA as a function of the voltage for different electrolyte compositions that contain FEC in the voltage range of 4.0 V to 4.4 V. FIG 13A shows results for the first cycle to 4.4 V.
Figure 13B shows results for the second cycle.
during a first experiment.
during a first experiment.
during a second experiment.
during a second experiment.
FIGs. 48A, C, and E show results for the first cycle to 4.4 V. FIGs. 48B, D, and F show results for the second cycle to 4.4 V.
as a function of the voltage for different electrolyte systems, including systems containing DTD, in the voltage range of 4.0 V to 4.4 V during a first cycle.
as a function of the voltage for different electrolyte systems, including systems containing DTD, in the voltage range of 4.0 V to 4.4 V during a second cycle.
as a function of the voltage for different electrolyte systems, including systems containing LFO, in the voltage range of 4.0 V to 4.4 V during a first cycle.
as a function of the voltage for different electrolyte systems, including systems containing LFO, in the voltage range of 4.0 V to 4.4 V during a second cycle.
as a function of the voltage for different electrolyte systems, including systems containing LFO, in the voltage range of 4.0 V to 4.4 V during a first cycle.
as a function of the voltage for different electrolyte systems, including systems containing LFO, in the voltage range of 4.0 V to 4.4 V during a second cycle.
+ 1%
DTD.
LFO, 0.5% LFO
+ 1% VC + 1% FEC, 1.0% LFO + 1% VC + 1% FEC, and 1.5% LFO + 1% VC + 1% FEC.
LFO +
1% FEC, and 1% LFO + 1% VC + 1% FEC.
with a positive electrode made from NMC 622 with two different coatings.
from Guangzhou Tinci Materials Technology Co., Ltd. and Shenzhen Capchem Technology Co., Ltd.
DETAILED DESCRIPTION OF THE DISCLOSURE
Generally, the battery cells 106 provide electricity to power electronics of the electric vehicle 100 and to propel the electric vehicle 100 using the drive motor 102A and/or 102B. The electric vehicle 100 includes a large number of other components that are not described herein but known to one or ordinary skill. While the construct of the electric vehicle 100 of FIG. 1 is shown to have four wheels, differing electric vehicles may have fewer or more than four wheels. Further, differing types of electric vehicles 100 may incorporate the inventive concepts described herein, including motor cycles, aircraft, trucks, boats, train engines, among other types of vehicles. Certain parts created using embodiments of the present disclosure may be used in vehicle 100.
Side walls 204 may also contain an insulating layer or be formed out of a nonconductive or electrically insulating material, such as polypropylene, polyurethane, polyvinyl chlorine, another plastic, a nonconductive composite, or an insulated carbon fiber. One or more interconnect layers 230 may be positioned above the battery cells 206, with a top plate 210 positioned over the interconnect layer 230. The top plate 210 may either be a single plate or be formed from multiple plates.
3 illustrates a schematic of a lithium ion cell 300. Lithium ions 350 are dispersed throughout electrolyte 320, within container 360. Container 360 may be part of a battery cell. The lithium ions 350 migrate between positive electrode 330 and negative electrode 340. Separator 370 separates the negative electrode and positive electrode. Circuitry 310 connects the negative electrode and positive electrode.
or another sulfur-containing additive, and 3) prop-1-ene-1,3-sultone (PES) combined with DTD or another sulfur-containing additive. These two-additive electrolyte systems are paired with a positive electrode made from lithium nickel manganese cobalt oxide with the composition LNiMnyCo,02 (abbreviated NMC generally or NMCxyz where the x, y, and z are the molar ratios of nickel, manganese and cobalt respectively). In certain embodiments, the positive electrode is formed from NMC111, NMC532, NMC811, or NMC622. In certain embodiments, NMC 532 positive electrodes formed from single-crystal, micrometer-side particles, which resulted in an electrode with micrometer-size areas of continuous crystal lattice (or grains), have been shown to be particularly robust, in part because the materials and processing conditions result in larger grain sizes than using conventional materials and processing conditions.
compound to create more robust systems.
The negative electrode may be made from natural graphite, artificial graphite, or another material.
(with or without MA), these solvents are merely exemplary of other carbonate solvents in particular and to other non-aqueous solvents. EC and EMC solvents were used in the experiments to control the systems tested in order to understand the effects of the additives, electrodes, and addition of MA as a solvent. Electrolyte systems may therefore may use other carbonate solvents and/or other non-carbonate solvents, including propylene carbonate, ethylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, another carbonate solvent (cyclic or acyclic), another organic solvent, and/or another non-aqueous solvent. Solvents are present in concentrations greater than the additives, typically greater than 6% by weight.
Pre-Experimental Setup Although the battery systems themselves may be packaged differently according to the present disclosure, the experimental setup typically used machine made "pouch cells"
to systematically evaluate the battery systems using a common setup, including the two-additive electrolyte systems and the specific materials for use the positive and negative electrodes. All percentages mentioned within this disclosure are weight percentages unless otherwise specified. A person of skill in the art will appreciate that the type of additive to be used and the concentration to be employed will depend on the characteristics which are most desirably improved and the other components and design used in the lithium ion batteries to be made and will be apartment from this disclosure.
Pouch Cells
ethyl methyl carbonate, (2) 1.2M LiPF6 in 24% ethylene carbonate, 56% ethyl methyl carbonate, and 20% methyl acetate; or (3) 1.2M LiPF6 in 18% ethylene carbonate, 42% ethyl methyl carbonate, and 40% methyl acetate. To this electrolyte, the additive components were added at specified weight percentages.
and held at 1.5 V for 24 hours to allow for the completion of wetting. Then, pouch cells were subjected to the formation process. Unless specified otherwise, the formation process consisted of charging the pouch cells at 11 mA (C/20) to 4.2 V and discharging to 3.8 V.
C/x indicates the that the time to charge or discharge the cell at the current selected is x hours when the cell has its initial capacity. For example, C/20 indicates that a charge or discharge would take 20 hours. After formation, cells were transferred and moved into the glove box, cut open to release any generated gas and then vacuum sealed again and the appropriate experiments were performed.
Electrochemical Impedance Spectroscopy
at 10.0 0.1 C.
DTD + 1%
TTSPi (collectively, PES211), an increased impedance is observed. The positive electrode is single-crystal NMC 532 and the negative electrode is artificial graphite.
is 1.0 M LiPF6 in 30% ethylene carbonate and 70% ethyl methyl carbonate. FIG. 35A summarizes experimental impedance data, plotting the negative of the imaginary portion of the impedance against the real portion of the impedance for 1.0 M LiPF6 in 30% ethylene carbonate and 70%
ethyl methyl carbonate (control electrolyte); 1.2 M LiPF6 in 30% ethylene carbonate and 70%
ethyl methyl carbonate; control electrolyte + 1% LiP02F2; control electrolyte + 2% LiP02F2;
and 20% methyl acetate + 1% LiP02F2. FIG. 35B summarizes experimental impedance data, plotting the negative of the imaginary portion of the impedance against the real portion of the impedance for the control electrolyte (same control as for FIG. 35A), 2% VC, 2% VC + 1%
LiP02F2; 20% MA + 1% LiP02F2 +2% VC; PES211; and PES211 + 1% LiP02F2. FIG. 35C
summarizes experimental impedance data, plotting the negative of the imaginary portion of the impedance against the real portion of the impedance for the control electrolyte (same control as for FIG. 35A), 2% FEC, 2% FEC + 1% LiP02F2; 1% DTD; and 1% DTD + 1%
LiP02F2.
FIG. 35D summarizes experimental impedance data for the control electrolyte (same control as for FIG. 35A); 1.2 M LiPF6 in 30% ethylene carbonate and 70% ethyl methyl carbonate; 1%
LiP02F2; 2% LiP02F2; 20% MA + 1% LiP02F2; 2% VC; 2% VC + 1% LiP02F2; 20% MA +
1% LiP02F2 + 2% VC; PES211; PES211 + 1% LiP02F2; 2% FEC, 2% FEC + 1% LiP02F2;
1% DTD; and 1% DTD + 1% LiP02F2.
1%
VC + 1% FEC in an electrolyte solution of 1.2 M LiPF6 in 30% ethylene carbonate and 70%
ethyl methyl carbonate. The EIS measurements were taken after formation, at 3.8 V, and at C. The positive electrode is single-crystal NMC532 and the negative electrode is artificial graphite.
Ultrahigh Precision Cycling and Storage Experiments
UPHC is employed to measure the coulombic efficiency, charge endpoint capacity slippage and other parameters to an accuracy of 30 ppm, in the case of the coulombic efficiency.
Details of the UHPC procedure are described in in T. M. Bond, J. C. Burns, D. A. Stevens, H.
M. Dahn, and J. R. Dahn, Journal of the Electrochemical Society, 160, A521 (2013), which is incorporated herein in its entirety.
higher CE value indicates less electrolyte degradation in the cell. Coulombic inefficiency per hour (CIE/h) is a normalized (per hour) coulombic inefficiency where the coulombic inefficiency is defined as 1-CE. It is calculated by taking 1-CE and dividing by the time of the cycle for which the CE
was measured. Charge endpoint capacity motion (or slippage) tracks the parasitic reactions occurring at the positive electrode as well as the positive material mass loss, if any. Less motion is better and relates to less electrolyte oxidation. Normalized discharge capacity, or fade rate, is another important metric, with a lower fade rate desirable and normally indicative of a battery system with a longer lifetime. Delta V is calculated as the difference between the average charge voltage and average discharge voltage. Delta V change relates closely to polarization growth with lower Delta V change as cycling occurs is preferable. UHPC
measurements are particularly appropriate for comparing electrolyte compositions because it allows for the tracking of metrics with a higher accuracy and precision and allows for the evaluation of various degradation mechanisms in a relatively rapid fashion.
experiments comparing single-additive electrolyte systems with the novel two-additive electrolyte systems (VC + DTD and FEC + DTD) in a base electrolyte system containing 1.2M LiPF6 in 30%
ethylene carbonate and 70% ethyl methyl carbonate, using a positive electrode consisting of single-crystal NMC532 and a negative electrode consisting of artificial graphite. FIGs. 4A-J
illustrate benefits of two-additive systems of the present disclosure, specifically adding DTD
to an electrolyte system containing VC or FEC.
+ 1%
DTD. FIG. 4B illustrates coulombic efficiency (CE) versus cycle number for electrolyte systems including 1% DTD, 2% VC, and 2% VC + 1% DTD. FIG. 4C illustrates the capacity of the charge endpoint plotted versus cycle number for electrolyte systems including 1% DTD, 2% VC, and 2% VC + 1% DTD. FIG. 4D illustrates the discharge capacity versus cycle number for electrolyte systems including 1% DTD, 2% VC, and 2% VC + 1% DTD. FIG. 4E
illustrates the difference between average charge voltage and average discharge voltage versus cycle number for electrolyte systems including 1% DTD, 2% VC, and 2% VC + 1% DTD.
FIG. 4F
illustrates time normalized coulombic inefficiency per hour (CIE/h) versus cycle number for electrolyte systems including 1% DTD, 2% FEC, and 2% FEC + 1% DTD. FIG. 4G
illustrates coulombic efficiency (CE) versus cycle number for electrolyte systems including 1% DTD, 2% FEC, and 2% FEC + 1% DTD. FIG. 411 illustrates the capacity of the charge endpoint plotted versus cycle number for electrolyte systems including 1% DTD, 2% FEC, and 2% FEC
+ 1% DTD. FIG. 41 illustrates the discharge capacity verses cycle number for electrolyte systems including 1% DTD, 2% FEC, and 2% FEC + 1% DTD. FIG. 4J illustrates the difference between average charge voltage and average discharge voltage versus cycle number for electrolyte systems including 1% DTD, 2% FEC, and 2% FEC + 1% DTD.
+ DTD and FEC + DTD. The experimental data shows that adding DTD to an electrolyte system containing VC or FEC in a base electrolyte system containing 1.2M LiPF6 in 30%
ethylene carbonate and 70% ethyl methyl carbonate by weight increases the performance of electrolyte systems that contain only VC or FEC as additives. Specifically, FIGs. 4A-J
illustrate that two-additive systems containing (VC + DTD and FEC + DTD) have a higher CE
(lower electrolyte degradation in the cell) and lower charge endpoint motion (lower electrolyte degradation at the positive electrode) compared to systems without the additives, or with only one additive. Further, FIGs. 4A-J also show a desirable lower fade rate (Qa).
Thus, an electrolyte system with two additives (VC + DTD and/or FEC + DTD) performs better (in terms of CIE/h, CE, charge end point slippage) than an electrolyte system that only contains a single additive of DTD, VC, or FEC.
DTD, 2% FEC, 2% FEC + 1% DTD, 2% VC, and 2% VC + 1% DTD. FIG. 5B shows a summary of the last three cycles of the fractional slippage per hour for electrolyte systems including 1% DTD, 2%
FEC, 2% FEC + 1% DTD, 2% VC, and 2% VC + 1% DTD. FIG. 5C shows a summary of the last three cycles of the fractional fade per hour for 1% DTD, 2% FEC, 2% FEC +
1% DTD, 2% VC, and 2% VC + 1% DTD.
exhibit lower time normalize coulombic inefficiency (CIE/h), and lower fractional slippage per hour (meaning that these electrolyte systems have longer lifetimes) compared to systems that only contained one additional additive-2% FEC, 2% VC, or 1% DTD. FIGs. 5A and 5B show that 1% DTD without another additive shows the highest CIE/h and fractional slippage.
However, when DTD is combined with VC or FEC, the two additives form a previously unexpected, synergistic effect causing the CIE/h and fractional slippage to be less in the two-additive electrolyte system compared to either single additive. FIG. 5C shows that the presence of 1% DTD decreases the fractional fade per hour, either as a single additive or as part of a two-additive electrolyte system with VC or FEC. This indicates that DTD is an important additive for increasing lifetime of the battery systems of the current invention. In addition to DTD, other sulfur-containing compounds can function in a similar manner and increase battery lifetime.
illustrate typical data collected during some of the ultra-high-precision-charging experiments that show that methyl acetate can be added to electrolyte systems containing VC or FEC with DTD to increase electrolyte conductivity and lower viscosity without sacrificing much lifetime. Increasing conductivity and decreasing viscosity is important for certain applications requiring a faster rate of charge.
LiPF6 in 30%
ethylene carbonate and 70% ethyl methyl carbonate; 2% FEC in a base electrolyte of 1.2M
LiPF6 in 24% ethylene carbonate, 56% ethyl methyl carbonate, and 20% methyl acetate; 2%
FEC + 1% DTD in a base electrolyte of 1.2M LiPF6 in 24% ethylene carbonate, 56% ethyl methyl carbonate, and 20% methyl acetate; 2% FEC in a base electrolyte of 1.2M
LiPF6 in 18%
ethylene carbonate, 42% ethyl methyl carbonate, and 40% methyl acetate; and 2%
FEC + 1%
DTD in a base electrolyte of 1.2M LiPF6 in 18% ethylene carbonate, 42% ethyl methyl carbonate, and 40% methyl acetate.
LiPF6 in 30% ethylene carbonate and 70% ethyl methyl carbonate; 2% FEC in a base electrolyte of 1.2M LiPF6 in 24% ethylene carbonate, 56% ethyl methyl carbonate, and 20%
methyl acetate; 2% FEC + 1% DTD in a base electrolyte of 1.2M LiPF6 in 24%
ethylene carbonate, 56% ethyl methyl carbonate, and 20% methyl acetate; 2% FEC in a base electrolyte of 1.2M LiPF6 in 18% ethylene carbonate, 42% ethyl methyl carbonate, and 40%
methyl acetate; and 2% FEC + 1% DTD in a base electrolyte of 1.2M LiPF6 in 18%
ethylene carbonate, 42% ethyl methyl carbonate, and 40% methyl acetate.
LiPF6 in 30%
ethylene carbonate and 70% ethyl methyl carbonate; 2% FEC in a base electrolyte of 1.2M
LiPF6 in 24% ethylene carbonate, 56% ethyl methyl carbonate, and 20% methyl acetate; 2%
FEC + 1% DTD in a base electrolyte of 1.2M LiPF6 in 24% ethylene carbonate, 56% ethyl methyl carbonate, and 20% methyl acetate; 2% FEC in a base electrolyte of 1.2M
LiPF6 in 18%
ethylene carbonate, 42% ethyl methyl carbonate, and 40% methyl acetate; and 2%
FEC + 1%
DTD in a base electrolyte of 1.2M LiPF6 in 18% ethylene carbonate, 42% ethyl methyl carbonate, and 40% methyl acetate.
in a base electrolyte of 1.2M LiPF6 in 30% ethylene carbonate and 70% ethyl methyl carbonate; 2% FEC
+ 1% DTD in a base electrolyte of 1.2M LiPF6 in 30% ethylene carbonate and 70%
ethyl methyl carbonate; 2% FEC in a base electrolyte of 1.2M LiPF6 in 24% ethylene carbonate, 56% ethyl methyl carbonate, and 20% methyl acetate; 2% FEC + 1% DTD in a base electrolyte of 1.2M LiPF6 in 24% ethylene carbonate, 56% ethyl methyl carbonate, and 20%
methyl acetate; 2% FEC in a base electrolyte of 1.2M LiPF6 in 18% ethylene carbonate, 42% ethyl methyl carbonate, and 40% methyl acetate; and 2% FEC + 1% DTD in a base electrolyte of 1.2M LiPF6 in 18% ethylene carbonate, 42% ethyl methyl carbonate, and 40%
methyl acetate.
ethylene carbonate and 70% ethyl methyl carbonate; 2% VC in a base electrolyte of 1.2M LiPF6 in 24% ethylene carbonate, 56% ethyl methyl carbonate, and 20% methyl acetate;
2% VC +
1% DTD in a base electrolyte of 1.2M LiPF6 in 24% ethylene carbonate, 56%
ethyl methyl carbonate, and 20% methyl acetate; 2% VC in a base electrolyte of 1.2M LiPF6 in 18% ethylene carbonate, 42% ethyl methyl carbonate, and 40% methyl acetate; and 2% VC + 1%
DTD in a base electrolyte of 1.2M LiPF6 in 18% ethylene carbonate, 42% ethyl methyl carbonate, and 40% methyl acetate.
LiPF6 in 30% ethylene carbonate and 70% ethyl methyl carbonate; 2% VC in a base electrolyte of 1.2M LiPF6 in 24% ethylene carbonate, 56% ethyl methyl carbonate, and 20%
methyl acetate; 2% VC + 1% DTD in a base electrolyte of 1.2M LiPF6 in 24% ethylene carbonate, 56% ethyl methyl carbonate, and 20% methyl acetate; 2% VC in a base electrolyte of 1.2M
LiPF6 in 18% ethylene carbonate, 42% ethyl methyl carbonate, and 40% methyl acetate; and 2% VC + 1% DTD in a base electrolyte of 1.2M LiPF6 in 18% ethylene carbonate, 42% ethyl methyl carbonate, and 40% methyl acetate.
ethylene carbonate and 70% ethyl methyl carbonate; 2% VC in a base electrolyte of 1.2M LiPF6 in 24% ethylene carbonate, 56% ethyl methyl carbonate, and 20% methyl acetate;
2% VC +
1% DTD in a base electrolyte of 1.2M LiPF6 in 24% ethylene carbonate, 56%
ethyl methyl carbonate, and 20% methyl acetate; 2% VC in a base electrolyte of 1.2M LiPF6 in 18% ethylene carbonate, 42% ethyl methyl carbonate, and 40% methyl acetate; and 2% VC + 1%
DTD in a base electrolyte of 1.2M LiPF6 in 18% ethylene carbonate, 42% ethyl methyl carbonate, and 40% methyl acetate.
in a base electrolyte of 1.2M LiPF6 in 30% ethylene carbonate and 70% ethyl methyl carbonate; 2% VC
+ 1% DTD in a base electrolyte of 1.2M LiPF6 in 30% ethylene carbonate and 70%
ethyl methyl carbonate; 2% VC in a base electrolyte of 1.2M LiPF6 in 24% ethylene carbonate, 56%
ethyl methyl carbonate, and 20% methyl acetate; 2% VC + 1% DTD in a base electrolyte of 1.2M LiPF6 in 24% ethylene carbonate, 56% ethyl methyl carbonate, and 20%
methyl acetate;
2% VC in a base electrolyte of 1.2M LiPF6 in 18% ethylene carbonate, 42% ethyl methyl carbonate, and 40% methyl acetate; and 2% VC + 1% DTD in a base electrolyte of 1.2M LiPF6 in 18% ethylene carbonate, 42% ethyl methyl carbonate, and 40% methyl acetate.
as an electrolyte solvent does not significantly sacrifice the overall performance of the battery system and as the long-term-cycling and plating experiments to be described later will show, it increases lifetime under higher charging rates. In particular, the performance of the two-additive electrolyte systems of the present disclosure are not sacrificed with the addition of MA
as a solvent. FIGs. 10A-C show the average of three last cycles of data generated during the experiments shown in FIGs. 9A-I. FIGs. 10A-C confirm that the addition of MA
as an electrolyte solvent does not significantly sacrifice the overall performance of the battery systems of the present disclosure that include two-additive electrolyte systems.
experiments that show that LFO generally performs well in electrolyte systems such that the properties of the systems perform well compared to the control electrolyte.
dramatically improves storage. Voltage drop is dramatically reduced, gassing is dramatically reduced and impedance is dramatically reduced after storage when LFO is added. LFO is effective in the presence of MA as well. FIGs. 38A-F show similar results in when LFO is added in electrolytes based on EC/DMC. When a good additive package like 1% FEC + 1% DTD is used, then the additional benefits brought by LFO are small. However, DTD-based electrolyte systems may be removed in the future because they often will change color over time when mixed and stored in a glove box.
VC + 1% DTD system. FIGs. 56A-C shows the results of additional experiments for CIE, fractional fade, and fractional slippage. The electrolyte system of 2% VC + 1%
DTD performs very well. Electrolyte systems of 1% LFO + 2% VC and 1% LFO + 1% VC + 1% FEC
also perform well (although not quite as good as the 2% VC + 1% DTD system). This experimental data agrees with the TAM experimental data.
systems generally perform well. FIGs. 58A-D summarize experimental data for electrolyte systems containing LFO with a positive electrode made from NMC 622 with two different coatings, indicated as A and B. For the different electrolyte systems studied, LFO has the impact of decreasing the voltage drop and also the impedance of the system.
Long Term Cycling
(C/20) to 4.2 V and discharged to 3.8 V. Cells were transferred and moved into the glove box, cut open to release gas generated and then vacuum sealed again. After formation, cells were cycled on a Neware charging systems. Cells were housed in a temperature controlled box at 40 C +/- 0.2 C or 20 C +/- 0.2 C. The cells were cycled between 3.0 V and the top of charge (4.2 V or 4.3 V) with a current of C/3 (half cycle of 3h) and a constant voltage step at the top of charge until the current dropped below C/20. Every 50 cycles, cells underwent one full cycle at C/20.
FIGs. 6A-F illustrate the advantage of two-additive electrolyte systems of the present disclosure, specifically, electrolytes that include DTD with VC or FEC. FIG.
6A shows experimental data of capacity versus cycle number for electrolyte systems including 1% DTD, 2% FEC, 2% FEC + 1% DTD, 2% VC, and 2% VC + 1% DTD, cycling between 3.0 V and 4.2 V. FIG. 6B shows experimental data of normalized capacity versus cycle number for electrolyte systems including 1% DTD, 2% FEC, 2% FEC + 1% DTD, 2% VC, and 2%
VC +
1% DTD, cycling between 3.0 V and 4.2 V. FIG. 6C shows experimental data of voltage hysteresis (difference between average charge voltage and average discharge voltage) versus cycle number for electrolyte systems including 1% DTD, 2% FEC, 2% FEC + 1%
DTD, 2%
VC, and 2% VC + 1% DTD, cycling between 3.0 V and 4.2 V. FIG. 6D shows experimental data of capacity versus cycle number for electrolyte systems including 1% DTD, 2% FEC, 2%
FEC + 1% DTD, 2% VC, and 2% VC + 1% DTD, cycling between 3.0 V and 4.2 V. FIG.
shows experimental data of normalized capacity versus cycle number for electrolyte systems including 1% DTD, 2% FEC, 2% FEC + 1% DTD, 2% VC, and 2% VC + 1% DTD, cycling between 3.0 V and 4.2 V. FIG. 6F shows experimental data of voltage hysteresis versus cycle number for electrolyte systems including 1% DTD, 2% FEC, 2% FEC + 1% DTD, 2%
VC, and 2% VC + 1% DTD, cycling between 3.0 V and 4.2 V. The experimental data shows that the two-additive electrolyte systems (DTD + FEC and DTD + VC) experience less capacity loss when cycling to 4.2 or 4.3 V and also lower polarization growth compared to the single additive electrolyte systems of VC or FEC.
FIGs. 7A-F
confirm that the advantages seen at 40 C are still present at lower temperatures, 20 C in this case. FIG. 7A shows experimental data of capacity versus cycle number for electrolyte systems including 1% DTD, 2% FEC, 2% FEC + 1% DTD, 2% VC, and 2% VC + 1% DTD, cycling between 3.0 V and 4.3 V. FIG. 7B shows experimental data of normalized capacity versus cycle number for electrolyte systems including 1% DTD, 2% FEC, 2% FEC + 1%
DTD, 2%
VC, and 2% VC + 1% DTD, cycling between 3.0 V and 4.3 V. FIG. 7C shows experimental data of voltage hysteresis (difference between average charge voltage and average discharge voltage) versus cycle number for electrolyte systems including 1% DTD, 2% FEC, 2% FEC +
1% DTD, 2% VC, and 2% VC + 1% DTD, cycling between 3.0 V and 4.3 V. FIG. 7D
shows experimental data of capacity versus cycle number for electrolyte systems including 1% DTD, 2% FEC, 2% FEC + 1% DTD, 2% VC, and 2% VC + 1% DTD, cycling between 3.0 V and 4.3 V. FIG. 7E shows experimental data of normalized capacity versus cycle number for electrolyte systems including 1% DTD, 2% FEC, 2% FEC + 1% DTD, 2% VC, and 2%
VC +
1% DTD, cycling between 3.0 V and 4.3 V. FIG. 7F shows experimental data of voltage hysteresis (difference between average charge voltage and average discharge voltage) versus cycle number for electrolyte systems including 1% DTD, 2% FEC, 2% FEC + 1%
DTD, 2%
VC, and 2% VC + 1% DTD, cycling between 3.0V and 4.3V. FIGs. 7A-F confirm the advantages of including DTD in the electrolyte with VC or FEC, especially when cycling occurs up to 4.3 V.
when long-term cycling at 20 C. FIGs. 7A-F show that the inclusion of DTD with VC or FEC
as part of a two-additive electrolyte system and cycling at 20 C, leads to less capacity loss at 4.2 V (slightly) and 4.3 V (more significantly) and lowers polarization growth. Thus, at either 20 C or 40 C, two-additive systems including DTD with VC or FEC improves the battery system by reducing the capacity loss and lowering the polarization growth.
+
1% MMDS, and 2% FEC + 1% MMDS, cycling between 3.0 V and 4.3 V at 40 C in a base electrolyte of 1.2M LiPF6 in 30% ethylene carbonate and 70% ethyl methyl carbonate. FIG.
8B shows experimental data of normalized capacity versus cycle number for electrolyte systems including 2% FEC, 1% FEC + 1% DTD, 2% FEC + 1% DTD, 1% FEC + 1% MMDS, and 2% FEC + 1% MMDS, cycling between 3.0 V and 4.3 V at 40 C in a base electrolyte of 1.2M LiPF6 in 30% ethylene carbonate and 70% ethyl methyl carbonate. FIG. 8C
shows experimental data of voltage hysteresis (difference between average charge voltage and average discharge voltage) versus cycle number for electrolyte systems including 2% FEC, 1%
FEC + 1% DTD, 2% FEC + 1% DTD, 1% FEC + 1% MMDS, and 2% FEC + 1% MMDS, cycling between 3.0 V and 4.3 V at 40 C in a base electrolyte of 1.2M LiPF6 in 30% ethylene carbonate and 70% ethyl methyl carbonate. FIG. 8D shows experimental data of peak capacity versus cycle number for electrolyte systems including 2% VC, 1% VC + 1% DTD, 2% VC +
1% DTD, 1% VC + 1% MMDS, and 2% VC + 1% MMDS, cycling between 3.0 V and 4.3 V
at 40 C in a base electrolyte of 1.2M LiPF6 in 30% ethylene carbonate and 70%
ethyl methyl carbonate. FIG. 8E shows experimental data of normalized capacity versus cycle number for electrolyte systems including 2% VC, 1% VC + 1% DTD, 2% VC + 1% DTD, 1% VC +
1%
MMDS, and 2% VC + 1% MMDS, cycling between 3.0 V and 4.3 V at 40 C in a base electrolyte of 1.2M LiPF6 in 30% ethylene carbonate and 70% ethyl methyl carbonate. FIG.
8F shows experimental data of voltage hysteresis (difference between average charge voltage and average discharge voltage) versus cycle number for electrolyte systems including 2% FEC, 1% VC + 1% DTD, 2% VC + 1% DTD, 1% VC + 1% MMDS, and 2% VC + 1% MMDS, cycling between 3.0 V and 4.3 V at 40 C in a base electrolyte of 1.2M LiPF6 in 30% ethylene carbonate and 70% ethyl methyl carbonate by weight. FIG. 8G shows experimental data of peak capacity versus cycle number for electrolyte systems including 2% PES, 1%
PES + 1%
DTD, 2% PES + 1% DTD, 1% PES + 1% MMDS, and 2% PES + 1% MMDS, cycling between 3.0 V and 4.3 V at 40 C in a base electrolyte of 1.2M LiPF6 in 30% ethylene carbonate and 70% ethyl methyl carbonate. FIG. 811 shows experimental data of normalized capacity versus cycle number for electrolyte systems including 2% PES, 1% PES + 1% DTD, 2% PES
+ 1%
DTD, 1% PES + 1% MMDS, and 2% PES + 1% MMDS, cycling between 3.0 V and 4.3 V
at 40 C in a base electrolyte of 1.2M LiPF6 in 30% ethylene carbonate and 70%
ethyl methyl carbonate. FIG. 81 shows experimental data of voltage hysteresis (difference between average charge voltage and average discharge voltage) for electrolyte systems including 2% FEC, 1%
PES + 1% DTD, 2% PES + 1% DTD, 1% PES + 1% MMDS, and 2% PES + 1% MMDS, cycling between 3.0 V and 4.3 V at 40 C in a base electrolyte of 1.2M LiPF6 in 30% ethylene carbonate and 70% ethyl methyl carbonate. FIGs. 8A-I illustrate that NMC532 performs well with two-additive electrolyte systems of 1% DTD with 1% VC, 2% VC, 1% FEC, or 2 FEC.
DTD performed better as an additive with VC or FEC than did MMDS.
and 16A-F
shows the results of experiments run at 20 C and 40 C, respectively. Cells with DTD performed better than cells without DTD in cells containing MA as a solvent.
LiPF6 in 30%
ethylene carbonate and 70% ethyl methyl carbonate; 1% FEC + 1% DTD in a base electrolyte of 1.2M LiPF6 in 30% ethylene carbonate and 70% ethyl methyl carbonate; 2% FEC
in a base electrolyte of 1.2M LiPF6 in 24% ethylene carbonate, 56% ethyl methyl carbonate, and 20%
methyl acetate; 2% FEC + 1% DTD in a base electrolyte of 1.2M LiPF6 in 24%
ethylene carbonate, 56% ethyl methyl carbonate, and 20% methyl acetate; 2% FEC in a base electrolyte of 1.2M LiPF6 in 18% ethylene carbonate, 42% ethyl methyl carbonate, and 40%
methyl acetate; and 2% FEC + 1% DTD in a base electrolyte of 1.2M LiPF6 in 18%
ethylene carbonate, 42% ethyl methyl carbonate, and 40% methyl acetate with cycling up to 4.2 V.
in a base electrolyte of 1.2M LiPF6 in 24% ethylene carbonate, 56% ethyl methyl carbonate, and 20% methyl acetate; 2% FEC + 1% DTD in a base electrolyte of 1.2M LiPF6 in 24%
ethylene carbonate, 56% ethyl methyl carbonate, and 20% methyl acetate; 2% FEC
in a base electrolyte of 1.2M LiPF6 in 18% ethylene carbonate, 42% ethyl methyl carbonate, and 40%
methyl acetate; and 2% FEC + 1% DTD in a base electrolyte of 1.2M LiPF6 in 18%
ethylene carbonate, 42% ethyl methyl carbonate, and 40% methyl acetate with cycling up to 4.2 V.
LiPF6 in 30%
ethylene carbonate and 70% ethyl methyl carbonate; 1% FEC + 1% DTD in a base electrolyte of 1.2M LiPF6 in 30% ethylene carbonate and 70% ethyl methyl carbonate; 2% FEC
in a base electrolyte of 1.2M LiPF6 in 24% ethylene carbonate, 56% ethyl methyl carbonate, and 20%
methyl acetate; 2% FEC + 1% DTD in a base electrolyte of 1.2M LiPF6 in 24%
ethylene carbonate, 56% ethyl methyl carbonate, and 20% methyl acetate; 2% FEC in a base electrolyte of 1.2M LiPF6 in 18% ethylene carbonate, 42% ethyl methyl carbonate, and 40%
methyl acetate; and 2% FEC + 1% DTD in a base electrolyte of 1.2M LiPF6 in 18%
ethylene carbonate, 42% ethyl methyl carbonate, and 40% methyl acetate with cycling up to 4.2 V.
LiPF6 in 30%
ethylene carbonate and 70% ethyl methyl carbonate; 1% FEC + 1% DTD in a base electrolyte of 1.2M LiPF6 in 30% ethylene carbonate and 70% ethyl methyl carbonate; 2% FEC
in a base electrolyte of 1.2M LiPF6 in 24% ethylene carbonate, 56% ethyl methyl carbonate, and 20%
methyl acetate; 2% FEC + 1% DTD in a base electrolyte of 1.2M LiPF6 in 24%
ethylene carbonate, 56% ethyl methyl carbonate, and 20% methyl acetate; 2% FEC in a base electrolyte of 1.2M LiPF6 in 18% ethylene carbonate, 42% ethyl methyl carbonate, and 40%
methyl acetate; and 2% FEC + 1% DTD in a base electrolyte of 1.2M LiPF6 in 18%
ethylene carbonate, 42% ethyl methyl carbonate, and 40% methyl acetate with cycling up to 4.3 V.
in a base electrolyte of 1.2M LiPF6 in 24% ethylene carbonate, 56% ethyl methyl carbonate, and 20% methyl acetate; 2% FEC + 1% DTD in a base electrolyte of 1.2M LiPF6 in 24%
ethylene carbonate, 56% ethyl methyl carbonate, and 20% methyl acetate; 2% FEC
in a base electrolyte of 1.2M LiPF6 in 18% ethylene carbonate, 42% ethyl methyl carbonate, and 40%
methyl acetate; and 2% FEC + 1% DTD in a base electrolyte of 1.2M LiPF6 in 18%
ethylene carbonate, 42% ethyl methyl carbonate, and 40% methyl acetate with cycling up to 4.3 V.
LiPF6 in 30%
ethylene carbonate and 70% ethyl methyl carbonate; 1% FEC + 1% DTD in a base electrolyte of 1.2M LiPF6 in 30% ethylene carbonate and 70% ethyl methyl carbonate; 2% FEC
in a base electrolyte of 1.2M LiPF6 in 24% ethylene carbonate, 56% ethyl methyl carbonate, and 20%
methyl acetate; 2% FEC + 1% DTD in a base electrolyte of 1.2M LiPF6 in 24%
ethylene carbonate, 56% ethyl methyl carbonate, and 20% methyl acetate; 2% FEC in a base electrolyte of 1.2M LiPF6 in 18% ethylene carbonate, 42% ethyl methyl carbonate, and 40%
methyl acetate; and 2% FEC + 1% DTD in a base electrolyte of 1.2M LiPF6 in 18%
ethylene carbonate, 42% ethyl methyl carbonate, and 40% methyl acetate with cycling up to 4.3 V.
with 20%
MA solvent shows very stable capacity retention at 4.3 V.
[00100] FIGs. 16A-F shows the results of experiments run at 40 C. Cells with DTD
performed better than cells without DTD in cells containing MA. FIG. 16A is a plot of experimental data taken at 40 C of capacity versus cycle number for electrolyte systems including 2% FEC in a base electrolyte of 1.2M LiPF6 in 30% ethylene carbonate and 70%
ethyl methyl carbonate; 1% FEC + 1% DTD in a base electrolyte of 1.2M LiPF6 in 30%
ethylene carbonate and 70% ethyl methyl carbonate; 2% FEC in a base electrolyte of 1.2M
LiPF6 in 24% ethylene carbonate, 56% ethyl methyl carbonate, and 20% methyl acetate; 2%
FEC + 1% DTD in a base electrolyte of 1.2M LiPF6 in 24% ethylene carbonate, 56% ethyl methyl carbonate, and 20% methyl acetate; 2% FEC in a base electrolyte of 1.2M
LiPF6 in 18%
ethylene carbonate, 42% ethyl methyl carbonate, and 40% methyl acetate; and 2%
FEC + 1%
DTD in a base electrolyte of 1.2M LiPF6 in 18% ethylene carbonate, 42% ethyl methyl carbonate, and 40% methyl acetate with cycling up to 4.2 V.
in a base electrolyte of 1.2M LiPF6 in 24% ethylene carbonate, 56% ethyl methyl carbonate, and 20% methyl acetate; 2% FEC + 1% DTD in a base electrolyte of 1.2M LiPF6 in 24%
ethylene carbonate, 56% ethyl methyl carbonate, and 20% methyl acetate; 2% FEC
in a base electrolyte of 1.2M LiPF6 in 18% ethylene carbonate, 42% ethyl methyl carbonate, and 40%
methyl acetate; and 2% FEC + 1% DTD in a base electrolyte of 1.2M LiPF6 in 18%
ethylene carbonate, 42% ethyl methyl carbonate, and 40% methyl acetate with cycling up to 4.2 V.
LiPF6 in 30%
ethylene carbonate and 70% ethyl methyl carbonate; 1% FEC + 1% DTD in a base electrolyte of 1.2M LiPF6 in 30% ethylene carbonate and 70% ethyl methyl carbonate; 2% FEC
in a base electrolyte of 1.2M LiPF6 in 24% ethylene carbonate, 56% ethyl methyl carbonate, and 20%
methyl acetate; 2% FEC + 1% DTD in a base electrolyte of 1.2M LiPF6 in 24%
ethylene carbonate, 56% ethyl methyl carbonate, and 20% methyl acetate; 2% FEC in a base electrolyte of 1.2M LiPF6 in 18% ethylene carbonate, 42% ethyl methyl carbonate, and 40%
methyl acetate; and 2% FEC + 1% DTD in a base electrolyte of 1.2M LiPF6 in 18%
ethylene carbonate, 42% ethyl methyl carbonate, and 40% methyl acetate with cycling up to 4.2 V.
LiPF6 in 30%
ethylene carbonate and 70% ethyl methyl carbonate; 1% FEC + 1% DTD in a base electrolyte of 1.2M LiPF6 in 30% ethylene carbonate and 70% ethyl methyl carbonate; 2% FEC
in a base electrolyte of 1.2M LiPF6 in 24% ethylene carbonate, 56% ethyl methyl carbonate, and 20%
methyl acetate; 2% FEC + 1% DTD in a base electrolyte of 1.2M LiPF6 in 24%
ethylene carbonate, 56% ethyl methyl carbonate, and 20% methyl acetate; 2% FEC in a base electrolyte of 1.2M LiPF6 in 18% ethylene carbonate, 42% ethyl methyl carbonate, and 40%
methyl acetate; and 2% FEC + 1% DTD in a base electrolyte of 1.2M LiPF6 in 18%
ethylene carbonate, 42% ethyl methyl carbonate, and 40% methyl acetate with cycling up to 4.3 V.
in a base electrolyte of 1.2M LiPF6 in 24% ethylene carbonate, 56% ethyl methyl carbonate, and 20% methyl acetate; 2% FEC + 1% DTD in a base electrolyte of 1.2M LiPF6 in 24%
ethylene carbonate, 56% ethyl methyl carbonate, and 20% methyl acetate; 2% FEC
in a base electrolyte of 1.2M LiPF6 in 18% ethylene carbonate, 42% ethyl methyl carbonate, and 40%
methyl acetate; and 2% FEC + 1% DTD in a base electrolyte of 1.2M LiPF6 in 18%
ethylene carbonate, 42% ethyl methyl carbonate, and 40% methyl acetate with cycling up to 4.3 V.
LiPF6 in 30%
ethylene carbonate and 70% ethyl methyl carbonate; 1% FEC + 1% DTD in a base electrolyte of 1.2M LiPF6 in 30% ethylene carbonate and 70% ethyl methyl carbonate; 2% FEC
in a base electrolyte of 1.2M LiPF6 in 24% ethylene carbonate, 56% ethyl methyl carbonate, and 20%
methyl acetate; 2% FEC + 1% DTD in a base electrolyte of 1.2M LiPF6 in 24%
ethylene carbonate, 56% ethyl methyl carbonate, and 20% methyl acetate; 2% FEC in a base electrolyte of 1.2M LiPF6 in 18% ethylene carbonate, 42% ethyl methyl carbonate, and 40%
methyl acetate; and 2% FEC + 1% DTD in a base electrolyte of 1.2M LiPF6 in 18%
ethylene carbonate, 42% ethyl methyl carbonate, and 40% methyl acetate with cycling up to 4.3 V.
concentration of less than 40%.
17B is a plot of experimental data of normalized capacity versus cycle number for electrolyte systems that contain FEC and/or DTD with cycling up to 4.3 V. FIG. 17C is a plot of experimental data of voltage hysteresis (difference between average charge voltage and average discharge voltage) versus cycle number for electrolyte systems that contain FEC and/or DTD with cycling up to 4.3 V. FIG. 17D is a plot of experimental data of capacity versus cycle number for electrolyte systems that contain VC and/or DTD with cycling up to 4.3 V. FIG.
17E is a plot of experimental data of normalized capacity versus cycle number for electrolyte systems that contain VC and/or DTD with cycling up to 4.3 V. FIG. 17F is a plot of experimental data of voltage hysteresis (difference between average charge voltage and average discharge voltage) versus cycle number for electrolyte systems that contain VC and/or DTD with cycling up to 4.3 V.
and FEC
+ DTD¨performs superior to any single additive of VC, FEC, or DTD.
shows capacity plotted versus cycle number. FIG. 18B shows normalized capacity plotted versus cycle number. FIG. 19 shows voltage hysteresis (difference between average charge voltage and average discharge voltage) versus cycle number. FIGs. 18A-B and 19 illustrate that the two-electrolyte additive system, including DTD + FEC improves performance over an electrolyte system that only includes FEC as an additive, but comparisons to FIGs. 6-F in which an artificial-graphite negative electrode was used, suggests that the performance of this specific artificial-graphite negative electrode outperforms this specific natural-graphite negative electrode in the two-additive electrolyte systems of the present disclosure.
summarizes data of fractional fade verses upper cut-off voltage for different electrolyte systems, including systems containing LFO. FIG. 41C summarizes data of charge-end-point capacity slippage verses upper cut-off voltage for different electrolyte systems, including systems containing LFO. FIG. 42A illustrates an expanded view of FIG. 41A and summarizes data of coulombic inefficiency verses upper cut-off voltage for different electrolyte systems, including systems containing LFO. FIG. 42B illustrates an expanded view of FIG. 41B and summarizes data of fractional fade verses upper cut-off voltage for different electrolyte systems, including systems containing LFO. FIG. 42C illustrates an expanded view of FIG. 41C and summarizes data of charge-end-point capacity slippage verses upper cut-off voltage for different electrolyte systems, including systems containing LFO. Adding LFO to control electrolyte vastly improves UHPC results. In the presence of MA, 1% LFO dramatically improves the situation compared to 0.5 % LFO. The CIE/h is about 4x10-5 h-1 for 1% LFO in control. By comparison, the best electrolyte systems without LFO, like 2% VC + 1% DTD in control are near 3x10-5 h-i.
data. In particular, 1% LFO added to the control electrolyte and to the electrolyte systems containing 20% MA improves the long-term cycling and impedance.
Microcalorimetry Measurements
The heat flow to the cell is a combination of three different effects: (1) ohmic heating, (2) entropy changes due to Li intercalating in the electrodes, and (3) parasitic reactions (electrolyte, including additive, degradation at either electrode). Because the test cells contain the same physical design, different only in the electrolyte, the difference in heat flow is primarily due to the differences in parasitic heat flow. Nevertheless, the parasitic heat flow can be extracted from the total heat flow using the procedures developed by Downie et al. (Journal of the Electrochemical Society, 161, A1782-A1787 (2014)) and by Glazier et al. (Journal of the Electrochemical Society, 164 (4) A567-A573 (2017)). Both of these references are incorporated herein in their entirety. Cells that have lower parasitic heat flow during cycling have better lifetimes. The voltage dependence of the parasitic reaction rate may be observed by plotting the measured parasitic heat flow as a function of cell voltage.
Instruments, stability +/- 0.0001 C, accuracy +/- 1 [LW, precision +/- 1 nW) at 40.0 C. The baseline drift over the course of the experiments did not exceed +/- 0.5 [LW. All specifications and information regarding microcalorimetry calibration, cell connections, and operation procedures can be found in previous literature. (For example, Downie et al, ECS
Electrochemical Letters 2, A106-A109 (2013).) Cells were cycled four times at a C/20 rate between 3.0 V and 4.2 V
to ensure well-formed, stable SEIs and were then charged between 4.0 V and different upper cut off limits at 1 mA to investigate the performance and the parasitic heat flow in different voltage ranges. Each pair of cells yielded near identical performance, so only one set of heat flow data is presented for each electrolyte.
1. Charge to 4.2 V, discharge to 4.0 V
2. Charge to 4.3 V, discharge to 4.0 V (repeat) 3. Charge to 4.4 V, discharge to 4.0 V (repeat) 6. Charge to 4.2 V, discharge to 4.0 V
Additional experimental detail is described in the Journal of the Electrochemical Society, 164 (4) A567-A573 (2017), which is incorporated herein by reference in its entirety.
Excluding additives, the electrolyte was either (1) 1.2M LiPF6 in 30% ethylene carbonate and 70% ethyl methyl carbonate, (2) 1.2M LiPF6 in 24% ethylene carbonate, 56%
ethyl methyl carbonate, and 20% methyl acetate; or (3) 1.2M LiPF6 in 18% ethylene carbonate, 42% ethyl methyl carbonate, and 40% methyl acetate, depending on the concentration of methyl acetate (0, 20, or 40%).
and B show experimental data (parasitic heat flow versus voltage) when charging to 4.4 V.
Since the charging to 4.4V was repeated, each plot shows the results of the one charging. The plot of the difference (lower plot in FIGs 11, 12A, 12B, 13A, and 13B) is calculated by taking the heat flow for each electrolyte mixture and subtracting the heat flow produced by the control (2% FEC). FIG. 14 shows a summary of the experimental data conveyed in FIGs.
11-13. Table 1 summarizes the data displayed in FIG. 14 in tabular form.
Table 1: Average Parasitic Heat Flow per Cycle (pW) (40. C, 4.0 V to UCV, 1 mA) Upper Cut Off 20 MA+ 2 Voltage 2 FEC Error FEC Error 40 MA +2 FEC Error 4.2 70.4 0.2 82 3 94 2 4.3 60.9 0.1 75 3 93 1 4.3 41.00 0.07 54 2 69.6 0.9 4.4 53.7 0.2 73 3 95 1 4.4 38.3 0.3 54 3 74.5 0.7 4.2 27.1 0.6 36 2 46.3 0.5 20 MA +2 2 FEC FEC 40 MA +2 FEC
1 DTD Error 1 DTD Error 1 DTD Error 4.2 63.9 0.2 69.7 0.3 77.3 0.3 4.3 54.7 0.3 64.9 0.7 76.95 0.07 4.3 36.8 0.2 46.5 0.3 58.6 0.1 4.4 48.4 0.5 65.0 0.6 84.7 0.1 4.4 34.6 0.4 49.1 0.6 66.0 0.2 4.2 24.44 0.04 31.4 0.3 39.3 0.7
FIGs. 48a-F show the result of the TAM experiments. The difference plots compare the system to 2% VC + 1%
DTD. FIGs. 48a-F show that 2% VC + 1DTD is better than 2% FEC + 1DTD. They also show that when optimizing for LFO within the system, 1% LFO + 1% VC + 1% FEC
is better than 2% VC + 1% DTD above 4.3 V. When comparing the systems with 1% LFO, 1%
LFO +
1% VC performs about as well as 1% LFO + 1% VC + 1% FEC and is better than 2%
VC +
1% DTD above 4.3 V. As observed in FIGs. 50A-C, the optimum LFO composition is about 1.0 %. FIG. 51 shows the mean parasitic heat flow as a function of cycles for the best performing cells. 0.5% LFO with 1% VC + 1% FEC is the best performing system after 4.4 V cycles. 2% VC + 1% LFO is very comparable to 2% VC + 1% DTD. Thus a system with VC and with or without DTD is possible.
Plating Experiments
Electrolyte systems that allow higher charging rates without plating are thus advantageous. To study plating on the negative electrode, plating experiments were performed.
Larger capacity loss indicates greater lithium plating.
measurements, cells were charged and discharged with constant currents (C-rates) of 1 C, 1.5 C, and 2.0 C between 2.8 and 4.1 V using a Maccor charger system at 20.0 0.1 C. Pair cells were tested for every charge rate to ensure reproducibility. In order to determine the active lithium loss during cycling, cells were cycled at C/20 one time before and after the high charge rate segments. The upper cutoff voltage was set to 4.1 V in order to minimize electrolyte oxidation at the positive electrode and to ensure that the cells were far from having a fully loaded negative electrode which would occur at 4.4 V for these cells. All pouch cells were cycled with external clamps to eliminate effects of small amounts of gas that may be produced during cycling. Cells were stopped after about 350 hours cycling or after the capacity loss reached 20%.
FIG. 22 indicates that addition of DTD does not significantly increase the maximum current at which plating occurs. For example, the low rate capacity loss of the electrolyte system consisting of two additives-2% FEC + 1% DTD¨is decreased compared to the electrolyte system consisting of the single additive 2% FEC at 1C, 1.5C, and 2C. Similarly, FIG. 22 shows that the low rate capacity loss of the electrolyte system consisting of two additives-1% FEC +
1% DTD¨is decreased compared to the electrolyte system consisting of the single additive 2% FEC at 1C
and 1.5C. It is also only slightly higher at 2C.
in retaining the peak capacity of the two-additive electrolyte system when DTD or MMDS were combined with VC.
27-34 illustrate the impact of using MA as a solvent in the presence of different electrolyte systems. FIG. 27 shows the results of plating experiments to determine the impact of MA as a solvent and the presence of DTD as an additive on the cell impedance. The electrolyte systems tested include 2% of an additive (VC, FEC, and PES) in an electrolyte with 0%, 20%, and 40%
MA. The remaining electrolyte for 0% MA is 1.2M LiPF6 in 30% ethylene carbonate and 70%
ethyl methyl carbonate. The remaining electrolyte for 20% MA is 1.2M LiPF6 in 24% ethylene carbonate and 56% ethyl methyl carbonate. The remaining electrolyte for 40% MA
is 1.2M
LiPF6 in 18% ethylene carbonate and 42% ethyl methyl carbonate. FIG. 28 is an expanded view of certain data shown in in FIG. 27 that had a small low rate capacity loss.
27 and 28 show that the presence of MA decreases the low rate capacity loss, even at charging rates of 2C. Thus, electrolyte systems containing 20% or 40% of MA are good candidates for use in applications that fast charging, such as energy storage in a vehicle that may be subjected to high charging current rates.
As can be seen from the experimental data the presence of MA reduces the amount of plating.
Further, LFO decreases the likelihood of Li-plating during high-rate charging.
For example, in FIG. 44A, the electrolyte system with 20%MA + 1% LFO showed significantly less loss of normalized discharge capacity than the other systems with either less MA or LFO. Loss of normalized discharge capacity is indicative of plating.
Gas Volume Measurements
During formation, cells are subject to a precisely controlled charge and discharge cycle, which is intended to activate the electrodes and electrolyte for use in their intended application.
During formation, gas is generated. If sufficient amounts of gas are generated (depending on the specific tolerances allowed by the cell and cell packaging), the gas may need to be released after the formation process and prior to application use. This typically requires the additional steps of breaking of a seal followed by a resealing. While these steps are common for many battery systems, it is desirable to remove them if possibly by choosing a system that produces less gas.
DTD and 2% FEC + 1% DTD. That is, DTD leads to higher gas volume production during formation, if DTD is to be used as an additive because of its desirable properties when combined with other additives, for example VC and FEC, then the system must include a mechanism to safely deal with the gas produced by the DTD, such as gas release after formation as discussed above.
FIG. 20 shows that two-additive electrolyte systems that include MMDS and PES
or FEC do not produce much (if any) additional gas than when 2% PES or FEC is the only additive.
25 shows the results of gas-generation experiments to determine the impact of MA as a solvent and presence of DTD as an additive on the formation gas generated. The electrolyte systems tested include 2% of an additive (VC, FEC, and PES) in an electrolyte with 0%, 20%, and 40%
MA. The remaining electrolyte for 0% MA is 1.2M LiPF6 in 30% ethylene carbonate and 70%
ethyl methyl carbonate. The remaining electrolyte for 20% MA is 1.2M LiPF6 in 24% ethylene carbonate and 56% ethyl methyl carbonate. The remaining electrolyte for 40% MA
is 1.2M
LiPF6 in 18% ethylene carbonate and 42% ethyl methyl carbonate.
is part of the two-additive electrolyte system compared to a one-additive electrolyte system that has only VC or FEC.
In-Situ Gas Volume Measurements
Cells with LFO, but no MA, show less gassing during hold segments of these tests.
Cell Impedance
DTD with 1%
or 2% of PES, FEC, or VC. FIG. 21 shows that these two-additive electrolyte systems of 1%
DTD with 1% or 2% of PES, FEC, or VC do not significantly increase the cell charge transfer impendence. In particular, systems of 1% DTD with 1% VC, 1% DTD with 2% VC, 1%
DTD
with 1% FEC, and 1% DTD with 2% FEC exhibit cell impedance values similar to the cell charge transfer impendence observed for the single-additive systems with DTD
excluded.
Therefore, these novel two-additive electrolyte systems do not sacrifice significant charge transfer impedance performance by including DTD.
26 shows the results of cell-charge transfer impedance experiments on electrolyte systems consisting of one- and two-additive systems with MA as one of the solvents.
The additive-electrolyte systems tested included 2% of additives VC, FEC, and PES without and without 1% DTD to show impact of the DTD and MA to the electrolyte system in an electrolyte solvent with 0%, 20%, and 40% MA. The electrolyte for 0% MA is 1.2M LiPF6 in 30%
ethylene carbonate and 70% ethyl methyl carbonate. The remaining electrolyte for 20% MA
is 1.2M
LiPF6 in 24% ethylene carbonate and 56% ethyl methyl carbonate. The remaining electrolyte for 40% MA is 1.2M LiPF6 in 18% ethylene carbonate and 42% ethyl methyl carbonate. FIG.
26 shows that DTD produces only slight increases in charge transfer impedance.
Further, in two-additive electrolyte systems that contain VC or FEC with DTD, the addition of MA
decreases cell charge transfer impedance. At 40% MA solvent, the VC + DTD and FEC + DTD
systems showed reduced charge transfer impedance from the corresponding systems without DTD and no MA as a solvent. In the PES + DTD two-additive electrolyte system, MA also reduced the charge transfer impedance of the system.
used to describe and claim the present disclosure are intended to be construed in a non-exclusive manner, namely allowing for items, components or elements not explicitly described also to be present.
Reference to the singular is also to be construed to relate to the plural.
Reference to "about" or "approximately" is to be construed to mean plus or minus 10%. Similarly, reference to any percentage of an additive is construed to mean plus or minus 10%.
Moreover, such joinder references do not necessarily infer that two elements are directly connected to each other.
Claims (19)
a negative electrode;
a positive electrode; and a nonaqueous electrolyte comprising lithium ions dissolved in a first nonaqueous solvent, and an additive mixture comprising:
a first operative additive of lithium difluorophosphate; and a second operative additive of either fluoro ethylene carbonate or vinylene carbonate.
a negative electrode;
a positive electrode comprising NMC with micrometer-scale grains; and a nonaqueous electrolyte comprising lithium ions dissolved in a first nonaqueous solvent, and an additive mixture comprising:
a first operative additive of either fluoro ethylene carbonate or vinylene carbonate; and a second operative additive of either 1,3,2-dioxathiolane-2,2-dioxide, another sulfur-containing additive, or lithium difluorophosphate.
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US15/663,976 | 2017-07-31 | ||
US15/663,976 US20190036171A1 (en) | 2017-07-31 | 2017-07-31 | Novel battery systems based on two-additive electrolyte systems |
US201762565985P | 2017-09-29 | 2017-09-29 | |
US62/565,985 | 2017-09-29 | ||
PCT/IB2018/055745 WO2019025980A1 (en) | 2017-07-31 | 2018-07-31 | Novel battery systems based on lithium difluorophosphate |
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JP (2) | JP2020529718A (en) |
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WO2020241438A1 (en) * | 2019-05-30 | 2020-12-03 | パナソニックIpマネジメント株式会社 | Non-aqueous electrolyte secondary battery |
JPWO2021039119A1 (en) * | 2019-08-30 | 2021-03-04 | ||
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JP2005011762A (en) * | 2003-06-20 | 2005-01-13 | Tdk Corp | Lithium ion secondary cell |
JP2006172775A (en) * | 2004-12-14 | 2006-06-29 | Hitachi Ltd | Energy storage device, its module and automobile using it |
JP4952186B2 (en) * | 2005-10-20 | 2012-06-13 | 三菱化学株式会社 | Non-aqueous electrolyte for secondary battery and secondary battery using the same |
JP5239119B2 (en) * | 2005-12-26 | 2013-07-17 | セントラル硝子株式会社 | Non-aqueous electrolyte battery electrolyte and non-aqueous electrolyte battery |
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