Non-aqueous solvent electrolyte formulations for energy storage devices
阅读说明：本技术 用于能量存储设备的非水溶剂电解质制剂 (Non-aqueous solvent electrolyte formulations for energy storage devices ) 是由 申俊昊 希厄·明赫·东 黃忠琼 于 2018-11-16 设计创作，主要内容包括：本文提供了改进的电解质制剂。改进的性能可以实现为改进的循环放电速率、改进的容量、改进的库仑效率或改进的循环容量。(Improved electrolyte formulations are provided herein. The improved performance may be realized as an improved cycling discharge rate, an improved capacity, an improved coulombic efficiency, or an improved cycling capacity.)
1. An energy storage device comprising:
a positive electrode including a positive active material;
an anode including an anode active material;
a separator between the positive electrode and the negative electrode; and
an electrolyte comprising a lithium salt and a nonaqueous electrolyte solvent formulation comprising Ethylene Carbonate (EC) and an additional solvent selected from at least one of Ethyl Methyl Carbonate (EMC), dimethyl carbonate (DMC), and Propylene Carbonate (PC), wherein the volume ratio of EC to the additional solvent is from about 1:2 to about 1: 4.
2. The energy storage device of claim 1, wherein the solvent comprises EC/EMC/DMC/PC in a volume ratio of 1:2:0.1: 0.02.
3. The energy storage device of claim 1, wherein the solvent comprises EC/DMC in a volume ratio of 1: 3.
4. The energy storage device of claim 1, wherein the solvent comprises an EC/EMC ratio of 1:2.4 by volume.
5. The energy storage device of claim 1, wherein the solvent comprises EC/EMC/DMC in a volume ratio of 1:0.5: 3.
6. The energy storage device of claim 1, wherein the solvent comprises EC/EMC/DMC in a volume ratio of 1:1: 1.
7. The energy storage device of claim 1, wherein the solvent comprises an EC/EMC ratio of 1:4 by volume.
8. The energy storage device of claim 1, wherein the solvent comprises EC/DMC in a volume ratio of 1: 4.
9. The energy storage device of claim 1, wherein the negative active material comprises natural graphite.
10. The energy storage device of claim 1, wherein the negative active material comprises surface modified artificial graphite.
11. The energy storage device of claim 1, wherein the negative active material comprises flake-shaped artificial graphite.
12. The energy storage device of claim 1, wherein the positive active material comprises layered lithium nickel manganese cobalt oxide (NMC).
13. The energy storage device of claim 1, wherein the positive active material comprises sulfur or a sulfur-containing material.
14. The energy storage device of claim 1, wherein the lithium salt is LiPF6。
15. The energy storage device of claim 1, wherein the energy storage device has a first charge capacity of at least about 150 mAh/g.
16. The energy storage device of claim 1, wherein the energy storage device has a first discharge capacity of at least about 100 mAh/g.
17. The energy storage device of claim 1, wherein the energy storage device has an efficiency of at least about 70%.
18. The energy storage device of claim 1, wherein the energy storage device has a capacity retention of at least about 80% after 500 cycles.
19. The energy storage device of claim 1, wherein the energy storage device has a charge capacity retention of at least about 94% at 1C.
20. The energy storage device of claim 1, wherein the energy storage device has a discharge capacity retention of at least about 65% at 1C.
21. A method of forming an energy storage device, the method comprising:
a housing is provided which is provided with a plurality of openings,
placing a positive electrode, a negative electrode, and a separator between the positive and negative electrodes into the casing, wherein at least one of the positive and negative electrodes is free of solvent residue; and
placing an electrolyte comprising a lithium salt and a non-aqueous electrolyte solvent formulation into the housing, the non-aqueous electrolyte solvent formulation comprising Ethylene Carbonate (EC) and an additional solvent selected from at least one of Ethyl Methyl Carbonate (EMC), dimethyl carbonate (DMC), and Propylene Carbonate (PC), wherein a volume ratio of EC to the additional solvent is from about 1:2 to about 1: 4.
Technical Field
The present invention relates generally to energy storage devices, and in particular to improved electrolyte formulations for use in energy storage devices.
Background
Electrical energy storage cells are widely used to provide electrical power to electronic, electromechanical, electrochemical and other useful devices. Such batteries include primary chemical batteries, secondary (rechargeable) batteries, fuel cells, and various capacitors, including supercapacitors. For enhancing energy storage, increasing power capacity, and broadening real life use cases, it is desirable to increase the operating voltage and temperature of an energy storage device that includes a capacitor.
Lithium ion batteries have been widely used as power sources in many commercial and industrial applications, such as consumer devices, production devices, and battery-powered vehicles. However, the demand for energy storage devices is continuing to increase rapidly. For example, the automotive industry is developing vehicles that rely on compact and efficient energy storage devices, such as plug-in hybrid vehicles and electric-only vehicles. Lithium ion batteries are well suited to meet future demands, however, there is a need for improved energy density to provide longer life batteries that can travel further in a single charge.
Electrolytes are one of the key components in conventional lithium ion batteries that determine the electrochemical performance and safety of these batteries. The compatibility between the electrodes and the electrolyte controls, in part, the performance of the battery. In addition, as the electrodes become thicker and/or heavier, the electrolyte system plays an important role in achieving high performance in the battery.
Disclosure of Invention
For purposes of summarizing the invention and the advantages achieved over the prior art, certain objects and advantages of the invention have been described herein. Not all of these objects or advantages may be achieved in any particular embodiment of the invention. Thus, for example, those skilled in the art will recognize that the invention may be embodied or carried out in a manner that achieves or optimizes one advantage or group of advantages as taught herein without necessarily achieving other objects or advantages as may be taught or suggested herein.
In a first aspect, an energy storage device may include an improved electrolyte formulation as provided herein. In some implementations, the energy storage device is a lithium ion battery.
One embodiment is an energy storage apparatus comprising: a positive electrode including a positive electrode active material; a negative electrode including a negative electrode active material; a separator (separator) between the positive electrode and the negative electrode; and an electrolyte comprising a lithium salt and a nonaqueous electrolyte solvent formulation comprising Ethylene Carbonate (EC) and an additional solvent selected from at least one of Ethyl Methyl Carbonate (EMC), dimethyl carbonate (DMC) and Propylene Carbonate (PC), wherein the volume ratio of EC to additional solvent is from about 1:2 to about 1: 4.
Another embodiment is a method of forming an energy storage device. The method can comprise the following steps: providing a casing into which a cathode, an anode, and a separator between the cathode and the anode are placed, wherein at least one of the cathode and the anode is free of solvent residues; and placing an electrolyte comprising a lithium salt and a nonaqueous electrolyte solvent formulation into the housing, the nonaqueous electrolyte solvent formulation comprising Ethylene Carbonate (EC) and an additional solvent selected from at least one of Ethyl Methyl Carbonate (EMC), dimethyl carbonate (DMC), and Propylene Carbonate (PC), wherein a volume ratio of EC to additional solvent is from about 1:2 to about 1: 4.
All such embodiments are intended to be within the scope of the invention herein disclosed. These and other embodiments of the present invention will become apparent to those skilled in the art from the following detailed description of the preferred embodiments having reference to the attached figures, the invention not being limited to any particular preferred embodiment disclosed.
Drawings
Fig. 1 depicts a longitudinal cross-sectional view showing an exemplary embodiment of an energy storage device with an improved electrolyte formulation.
Fig. 2 depicts an embodiment of an energy storage device with an improved electrolyte formulation.
Fig. 3A and 3B show the charge and discharge capacity (fig. 3A) and coulombic efficiency (fig. 3B) of the natural graphite electrode in the form of a half cell according to example 1.
Fig. 4A and 4B show the charge and discharge capacities of the artificial graphite electrode prepared by the dry cell battery electrode (fig. 4A)
Fig. 5 shows the charge and discharge capacity of the artificial graphite electrode prepared according to
Fig. 6A and 6B show the charge and discharge capacity (fig. 6A) and coulomb efficiency (fig. 6B) of the sheet-like artificial graphite electrode in the form of a half cell according to example 1.
Fig. 7A and 7B show the charge and discharge capacity (fig. 7A) and coulombic efficiency (fig. 7B) of the NMC/graphite full cell according to example 1.
Fig. 8A, 8B, 8C show the charge and discharge capacities (fig. 8A and 8B) and the coulombic efficiencies (fig. 8C) of the NMC 811/graphite full cell and the NMC 622/graphite full cell with electrolytes of
Fig. 9A and 9B show the (fig. 9A) discharge and (fig. 9B) charge capacity retention of an NMC 622/graphite full cell with the electrolyte of
Fig. 10A and 10B show the (fig. 10A) discharge and (fig. 10B) charge capacity retention of an NMC 622/graphite full cell with the electrolyte of
Detailed Description
Definition of
As used herein, the terms "battery" and "capacitor" will be given their ordinary and customary meaning to those of ordinary skill in the art. The terms "battery" and "capacitor" are non-exclusive of each other. A capacitor or battery may refer to a single electrochemical cell that may operate alone or as a component of a multi-cell system.
As used herein, the voltage of an energy storage device is the operating voltage of a single battery or capacitor cell. The voltage may exceed the rated voltage or be below the rated voltage under load, or according to manufacturing tolerances.
As provided herein, a "self-supporting" electrode film or active layer is an electrode film or layer that incorporates an adhesive matrix structure sufficient to support the film or layer and maintain its shape such that the electrode film or layer may be free-standing. When incorporated into an energy storage device, the self-supporting electrode film or active layer is one that incorporates such a binder matrix structure. Typically, such electrode films or active layers are strong enough to be employed in an energy storage device manufacturing process without any external support elements (such as current collectors or other films), depending on the method employed. For example, a "self-supporting" electrode film may have sufficient strength to be rolled, handled, and unrolled in an electrode manufacturing process without other supporting elements.
As provided herein, a "solvent-free" electrode film is an electrode film that does not contain detectable processing solvent, processing solvent residue, or processing solvent impurities. The processing solvent or conventional solvent includes an organic solvent. The dry electrode film (such as a positive electrode film or a negative electrode film) may be solvent-free.
A "wet" electrode or "wet process" electrode is an electrode prepared by at least one step involving a slurry of active material, binder, and processing solvent, processing solvent residue, and/or processing solvent impurities. The wet electrode may optionally include additives.
Description of the invention
Various embodiments of the present invention relate to electrolyte formulations for energy storage devices having improved performance. In one embodiment, the energy storage device may be a lithium ion based battery.
One embodiment is an energy storage device with an improved nonaqueous electrolyte solvent blend. The improved electrolyte may improve physical and chemical characteristics of the electrolyte, such as viscosity, wettability, and conductivity. The performance impact of the electrolyte can be attributed in part to physical properties such as viscosity and wettability, as well as chemical or electrochemical properties such as reactivity of the solvent on the electrode surface (e.g., graphite surface). The shape of the active material particles may also play a role. For example, the particles of graphite material may be spheroidal graphite (also known as "potato-shaped" graphite) or flake graphite.
In one embodiment, the electrolyte composition enhances the electrochemical performance of the electrode, particularly a dry-processed battery electrode. The present disclosure provides electrolyte compositions for relatively thick or highly loaded battery electrodes. The discharge rate performance of the improved electrolyte formulations provided herein can be compared to typical lithium ion battery electrolytes.
In one embodiment, the improved electrolyte formulation may include a lithium salt and an electrolyte solvent (such as a mixture of non-aqueous or organic solvents) and optionally one or more additives. For example, the improved electrolyte may include one or more carbonates, such as Ethylene Carbonate (EC), Propylene Carbonate (PC), ethylene carbonate (VEC), Vinylene Carbonate (VC), fluoroethylene carbonate (FEC), and combinations thereof. The electrolyte may also include one or more acyclic carbonates, such as dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl Methyl Carbonate (EMC), and combinations thereof.
Generally, the lithium salt may include a redox stable anion. In some embodiments, the anion can be monovalent. In some embodiments, the lithium salt may be selected from hexafluorophosphates (LiPF)6) Lithium tetrafluoroborate (LiBF)4) Lithium perchlorate (LiClO)4) Lithium bis (trifluoromethanesulfonyl) imide (LiN (SO)2CF3)2) Lithium trifluoromethanesulfonate (LiSO)3CF3) And combinations thereof. In some embodiments, the electrolyte may include a composition selected from the group consisting of hexafluorophosphates, tetrafluoroborates, and iodidesAn anion of the group (1). In some embodiments, the salt concentration may be from about 0.1mol/l (M) to about 5M, from about 0.2M to about 3M, or from about 0.3M to about 2M. In further embodiments, the salt concentration of the electrolyte may be about 0.7M to about 1M. In certain embodiments, the salt concentration of the electrolyte may be about 0.2M, about 0.3M, about 0.4M, about 0.5M, about 0.6M, about 0.7M, about 0.8M, about 0.9M, about 1M, about 1.1M, about 1.2M, or any range therebetween.
In some embodiments, an energy storage device electrolyte as provided herein can include a liquid solvent. The solvents provided herein need not dissolve every component of the electrolyte, and need not completely dissolve any component of the electrolyte. In a further embodiment, the solvent may be an organic solvent. In some embodiments, the solvent may include one or more functional groups selected from carbonates, ethers, and/or esters. In some embodiments, the solvent may comprise a carbonate as described herein. In further embodiments, the carbonate may be selected from cyclic carbonates (such as Ethylene Carbonate (EC), Propylene Carbonate (PC), ethylene carbonate (VEC), Vinylene Carbonate (VC), fluoroethylene carbonate (FEC), and combinations thereof), or acyclic carbonates (such as dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl Methyl Carbonate (EMC), and combinations thereof). In certain embodiments, the electrolyte may include LiPF6And one or more carbonates.
The electrolyte formulations provided herein can be further optimized by adjusting the individual solvent ratios in a given formulation. For example, the energy storage device may include a nonaqueous electrolyte solvent formulation including Ethylene Carbonate (EC) and at least one additional solvent. In one embodiment, the additional solvent may include Ethyl Methyl Carbonate (EMC), dimethyl carbonate (DMC) of Propylene Carbonate (PC). In some embodiments, wherein the volume ratio of EC to additional solvent is from about 1:2 to about 1:4, although other ranges are contemplated.
The electrolyte formulations provided herein can further include one or more additives. The additive may be, for example, a lithium salt or a liquid additive. An example of a lithium salt is LiClO4、LiBF4、CF3SO2NLiSO2CF3、C4F10LiNO4S2And combinations thereof, and at various salt concentration ratios. Additives may be selected to improve SEI formation and increase wetting rate and may also include, for example, vinylene carbonate, ethylene carbonate, fluoroethylene carbonate, cyclohexane, and the like. In some embodiments, the electrolyte formulation includes a lithium salt additive that is about 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 3%, 4%, or 5%, or any range therebetween.
In some embodiments, the electrolyte solvent may include an EC/EMC/DMC/PC solvent in a volume ratio of about 1:2:0.1: 0.02. In some embodiments, the electrolyte solvent comprises EC/DMC in a volume ratio of about 1: 3. In some embodiments, the electrolyte solvent comprises an EC/EMC ratio of about 1:3 by volume. In some embodiments, the electrolyte solvent comprises an EC/EMC ratio of about 1:2.4 by volume. In some embodiments, the electrolyte solvent comprises EC/EMC/DMC in a volume ratio of about 1:0.5: 3. In some embodiments, the electrolyte solvent comprises EC/EMC/DMC in a volume ratio of about 1:1: 1. In some embodiments, the electrolyte solvent comprises an EC/EMC ratio of about 1:4 by volume. In some embodiments, the electrolyte solvent comprises EC/DMC in a volume ratio of about 1: 4. In a further embodiment, the lithium salt is present in the electrolyte at a concentration of about 0.1M to about 2M. For example, the lithium salt may be present in the electrolyte at a concentration of about 1 to 1.3M. In a further embodiment, the lithium salt is LiPF6。
In some embodiments, energy storage devices including electrolyte formulations as provided herein can exhibit higher discharge rate capacities compared to energy storage devices that do not use the improved electrolyte formulations. Such higher discharge rate capability is desirable in high energy, high power applications, such as electric vehicle propulsion. In conventional lithium ion batteries, a discharge rate of less than about C/5, where C/5 is the discharge current relative to the battery capacity, can generally be managed by a higher energy electrode design, such that the battery is depleted within 5 hours. However, as electrodes become thicker (as associated with higher battery power), electrolyte formulations become increasingly important to address discharge performance at higher C-rates (above 1C). In some embodiments, the disclosed electrolyte formulations exhibit discharge performance advantages, providing higher energy retention at higher discharge currents. In some embodiments, the electrolyte formulations provided herein exhibit higher discharge rate capacities.
Energy storage devices comprising the electrolyte formulations described herein are characterized by improved capacity retention over the life of the device. Improved capacity retention may provide devices with improved power density over the life of the device. In further embodiments, energy storage devices comprising electrolytes provided herein can exhibit improved energy delivery at high C-rates. For example, improved energy delivery may be achieved at C-rates greater than 1. Some embodiments provide an energy storage device that exhibits improved coulombic efficiency (coulombiceficiency) relative to energy storage devices including typical electrolytes. Further improvements that may be realized in various embodiments include improved cycling performance, including improved storage stability during cycling, and reduced capacity fade.
The electrolyte solvent and/or the electrolyte additive may facilitate the formation of a Solid Electrolyte Interface (SEI) layer on the surface of the electrode. It is believed that the solid electrolyte interface may be formed in part due to decomposition of one or more components of the electrolyte. For example, a single-step or multi-step decomposition reaction that transfers electrons to one or more solid electrolyte interface-forming components of the electrolyte may result in the formation of a solid electrolyte interface at the interface between the anode and the electrolyte. Electrodes with solid electrolyte interface layers may exhibit lower operational negative electrode potentials and/or higher operational potentials for energy storage devices.
It should be understood that the electrolyte formulations provided herein may be used in various embodiments with any of a variety of energy storage devices and systems, such as one or more batteries, capacitors, capacitor-battery mixtures, fuel cells, or other energy storage systems or devices, and combinations thereof. In some embodiments, the electrolyte additive or electrolyte comprising the additives described herein can be implemented in a lithium ion battery.
An energy storage device as provided herein may have any suitable configuration, such as planar, spiral wound, button, or pouch. Energy storage devices provided herein can be components of systems such as power generation systems, uninterruptible power supply systems (UPS), photovoltaic power generation systems, energy recovery systems for industrial machinery and/or transportation, for example. The energy storage devices provided herein may be used to provide power to various electronic devices and/or motor vehicles, including Hybrid Electric Vehicles (HEVs), plug-in hybrid electric vehicles (PHEVs), and/or Electric Vehicles (EVs).
Fig. 1 shows a longitudinal cross-sectional view of an exemplary embodiment of an energy storage device. The device has a wound electrode unit 10 comprising a first collector sheet and a second collector sheet, impregnated with the improved electrolyte provided herein, and placed in a housing 30. The upper end of the housing 30 facing the
Fig. 2 illustrates a side cross-sectional schematic view of an example of an
The device has a first electrode 102, a second electrode 104, and a spacer 106 between the first electrode 102 and the second electrode 104. The first electrode 102 and the second electrode 104 are adjacent to respective opposing surfaces of the spacer 106. The
One or more of the first electrode 102, the second electrode 104, and the spacer 106, or a combination thereof, may include a porous material. The pores within the porous material may provide containment and/or increased surface area for contact with the modified electrolyte formulation 118 within the housing 120. The energy storage device housing 120 may be sealed around the first electrode 102, the second electrode 104, and the spacer 106, and may be physically sealed from the surrounding environment.
In some embodiments, the first electrode 102 may be a negative electrode ("negative electrode") and the second electrode 104 may be a positive electrode ("positive electrode"). The spacer 106 may be configured to electrically insulate two electrodes (such as the first electrode 102 and the second electrode 104) adjacent to opposite sides of the spacer 106, while allowing ionic communication between the two adjacent electrodes. The spacer 106 may comprise a suitable porous electrically insulating material. In some embodiments, the spacer 106 may comprise a polymeric material. For example, the spacer 106 may include a cellulosic material (e.g., paper), a Polyethylene (PE) material, a polypropylene (PP) material, and/or a polyethylene and polypropylene material.
In general, the first electrode 102 and the second electrode 104 each include a current collector and an electrode film. The electrodes 102 and 104 include high density electrode films 112 and 114, respectively. The high-density electrode films 112 and 114 can have any suitable shape, size, and thickness. For example, the electrode film can have a thickness of about 30 micrometers (μm) to about 250 micrometers, e.g., about 50 micrometers, about 100 micrometers, about 150 micrometers, about 200 micrometers, about 250 micrometers, about 300 micrometers, about 400 micrometers, about 500 micrometers, about 750 micrometers, about 1000 micrometers, about 2000 micrometers, or any range of values therebetween. The electrode film generally includes one or more active materials, such as a negative electrode active material or a positive electrode active material provided herein. Electrode films 112 and/or 114 can be dry and/or self-supporting electrode films as provided herein and have advantageous properties as provided herein, such as thickness, energy density, specific energy density, area energy, or area capacity. The first electrode film 112 and/or the second electrode film 114 can also include one or more adhesives as provided herein. Electrode films 112 and/or 114 can be prepared by processes described herein. Electrode films 112 and/or 114 may be wet electrodes or self-supporting dry electrodes as described herein.
As shown in fig. 2, the first electrode 102 and the second electrode 104 respectively include a first collector 108 in contact with a first high-density electrode film 112, and a second collector 110 in contact with a second high-density electrode film 114. The first current collector 108 and the second current collector 110 facilitate electrical coupling between each respective electrode film and an external circuit (not shown). First current collector 108 and/or second current collector 110 comprise one or more conductive materials and may have any suitable shape and size selected to facilitate the transfer of charge between the respective electrode and an external circuit. For example, the current collector may include metallic materials such as materials including aluminum, nickel, copper, rhenium, niobium, tantalum, and noble metals (such as silver, gold, platinum, palladium, rhodium, osmium, iridium), as well as alloys and combinations of the foregoing. For example, the first current collector 108 and/or the second current collector 110 may include, for example, aluminum foil or copper foil. The first current collector 108 and/or the second current collector 110 may have a rectangular or substantially rectangular shape sized to provide charge transfer between the respective electrodes and an external circuit.
In some embodiments,
In some embodiments, the lithium ion battery is configured to operate at about 2.5 to 4.5V or 3.0 to 4.2V. In further embodiments, the lithium ion batteries are configured to have a minimum operating voltage of about 2.5V to about 3V, respectively. In still further embodiments, the lithium ion batteries are configured to have a maximum operating voltage of about 4.1V to about 4.4V, respectively.
In some embodiments, an electrode film as provided herein comprises at least one active material and at least one binder. The at least one active material may be any active material known in the art. The at least one active material may be a material suitable for use in a negative electrode or a positive electrode of a battery.
In some embodiments, the electrode film of the lithium ion energy storage device may include a negative active material. In some embodiments, the negative active material may include, for example, an intercalation material (such as carbon, graphite, and/or graphene), an alloy/de-alloying material (such as silicon, silicon oxide, tin, and/or tin oxide), a metal alloy or compound (such as Si-Al and/or Si-Sn), and/or a conversion material (such as manganese oxide, molybdenum oxide, nickel oxide, and/or copper oxide). The negative active materials may be used alone or mixed together to form a multiphase material (such as Si-C, Sn-C, SiOx-C, SnOx-C, Si-Sn, Si-SiOx, Sn-SnOx, Si-SiOx-C, Sn-SnOx-C, Si-Sn-C, SiOx-SnOx-C, Si-SiOx-Sn, or Sn-SiOx-SnOx).
In some embodiments, the electrode films of the lithium ion energy storage device may include an active positive electrode material. In some embodiments, the positive active material may include, for example, a metal oxide, a metal sulfide, or a lithium metal oxide. The lithium metal oxide may be, for example, lithium nickel manganese cobalt oxide (NMC), Lithium Manganese Oxide (LMO), lithium iron phosphate (LFP), Lithium Cobalt Oxide (LCO), Lithium Titanate (LTO), and/or lithium nickel cobalt aluminum oxide (NCA). In some embodiments, the positive electrode active material may include, for example, a layered transition metal oxide (such as LiCoO)2(LCO)、Li(NiMnCo)O2(NMC) and/or LiNi0.8Co0.15Al0.05O2(NCA)), spinel manganese oxides (such as LiMn)2O4(LMO) and/or LiMn1.5Ni0.5O4(LMNO)), olivine (such as LiFePO)4) Silicon, silicon oxide (SiOx), aluminum, tin oxide (SnOx), manganese oxide (MnOx), molybdenum oxide (MoO)2) Molybdenum disulfide (MoS)2) Nickel oxide (NiOx) or copper oxide (CuOx). The positive electrode active material may include sulfur or a sulfur-containing material, such as lithium sulfide (Li)2S) or other sulfur-based materials, or mixtures thereofA compound (I) is provided. In some embodiments, the positive electrode membrane includes a material having a concentration of sulfur or sulfur-containing active material of at least 50 wt%. In some embodiments, the positive electrode film of a material comprising sulfur or a sulfur-containing active material further comprises a binder. In some embodiments, the binder of the positive electrode film of the material comprising sulfur or the sulfur-containing active material is selected from Polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), poly (ethylene oxide) (PEO), Polyethylene (PE), polyacrylic acid (PAA), gelatin, other thermoplastics, or any combination thereof.
The negative active material includes commonly used natural graphite, synthetic or artificial graphite, surface-modified graphite, spheroidal graphite, flake graphite, and blends or combinations of these types of graphite, metal elements and compounds thereof, and metal-C composites for negative electrodes.
As previously discussed herein, the type and shape of the negative active material and electrolyte solvent formulation used in the energy storage device may affect the performance of the energy storage device. The electrochemical performance of the negative electrode using a particular electrolyte formulation may be attributed to physical properties (such as viscosity and wettability) as well as chemical or electrochemical properties (such as reactivity of the solvent on the surface of the negative active material) of the electrolyte formulation. For example, the particle shape and particle size of graphite powder affects the surface area of the powder that can be used for the electrolyte. The varying amounts of surface area can affect the extent of irreversible electrochemical reactions of electrolyte components on the surface of the graphite particles. Without being bound by theory, solvolysis is believed to be the primary irreversible reaction that occurs on the graphite particles in the first lithiation process. Typical Li/Li of solvent+The reduction potential includes: EC 1.36V; DMC 1.32V; DEC 1.32V; EMC<1.32V; and PC ═ 1.0 to 1.6V.
Generally, plate-like particles have a larger surface area relative to their volume than spherical particles. Furthermore, in some embodiments, the use of cyclic carbonates (e.g., EC) in the electrolyte formulation may result in an increase in the viscosity of the solvent mixture. In some embodiments, the increased viscosity of the electrolyte results in a stable solid phase interface (SEI) on the graphite particles operating at relatively low voltages. In some embodiments, the use of a linear carbonate (e.g., DMC) in the electrolyte formulation results in a decrease in the viscosity of the solvent mixture. In some embodiments, the reduced electrolyte viscosity results in improved ionic conductivity of the electrolyte solution.
In some embodiments, EC-based and EMC-rich electrolyte formulations used with spheroidal graphite anode active materials exhibit improved electrochemical performance. In some embodiments, EC-based and EMC-rich electrolyte formulations used with natural graphite anode active materials exhibit improved electrochemical performance. In some embodiments, EC-based and EMC-rich electrolyte formulations used with surface-modified artificial graphite anode active materials exhibit improved electrochemical performance. In some embodiments, EC-based and EMC-rich electrolyte formulations used with flake-like artificial graphite anode active materials exhibit improved electrochemical performance. In some embodiments, EC-based and DMC-rich electrolyte formulations used with graphite flake anode active materials exhibit improved electrochemical performance. In some embodiments, EC-based and DMC-rich electrolyte formulations used with flake-like artificial graphite anode active materials exhibit improved electrochemical performance.
The at least one active material may include one or more carbon materials. The carbon material may be selected from, for example, a graphitic material, graphite, graphene-containing material, hard carbon, soft carbon, carbon nanotubes, porous carbon, conductive carbon, or combinations thereof. The activated carbon may be derived from a vapor process or an acid/etch process. In some embodiments, the graphite material may be a surface treated material. In some embodiments, the porous carbon may comprise activated carbon. In some embodiments, the porous carbon may comprise a layered structure carbon. In some embodiments, the porous carbon may include structured carbon nanotubes, structured carbon nanowires, and/or structured carbon nanoplatelets. In some embodiments, the porous carbon may comprise graphene sheets. In some embodiments, the porous carbon may be surface treated carbon.
In some embodiments, a positive electrode film of a lithium ion battery or hybrid energy storage device may include from about 70 wt% to about 98 wt% of at least one active material comprising: from about 70 wt% to about 92 wt%, or from about 70 wt% to about 96 wt%. In some embodiments, the positive electrode membrane may include up to about 10 wt% of a porous carbon material comprising: up to about 5 wt%, or about 1 wt% to about 5 wt%. In some embodiments, the positive electrode film comprises up to about 5 wt% of a conductive additive comprising: from about 1% to about 3% by weight. In some embodiments, the positive electrode film includes up to about 20 wt% binder, such as about 1.5 wt% to 10 wt%, about 1.5 wt% to 5 wt%, or about 1.5 wt% to 3 wt%. In some embodiments, the positive electrode film comprises from about 1.5% to about 3% by weight of the binder.
In some embodiments, the negative electrode film may include at least one active material, a binder, and optionally a conductive additive. In some embodiments, the conductive additive may include a conductive carbon additive, such as carbon black. In some embodiments, the at least one active material of the negative electrode may include synthetic graphite, natural graphite, hard carbon, soft carbon, graphene, mesoporous carbon, silicon oxide, tin oxide, germanium, lithium titanate, mixtures or composites of the foregoing. In some embodiments, the negative electrode film may include about 80 wt% to about 98 wt% of at least one active material comprising: from about 80 wt% to about 98 wt%, or from about 94 wt% to about 97 wt%. In some embodiments, the negative electrode film comprises up to about 5 wt% of a conductive additive comprising: from about 1% to about 3% by weight. In some embodiments, the negative electrode film comprises up to about 20 wt% of a binder comprising: about 1.5 wt% to 10 wt%, about 1.5 wt% to 5 wt%, or about 3 wt% to 5 wt%. In some embodiments, the negative electrode film includes about 4 wt% of the binder. In some embodiments, the anode film may not include a conductive additive.
Some embodiments include an electrode film having one or more active layers including a polymeric binder material, such as an electrode film of a negative electrode and/or a positive electrode. The binder may include Polytetrafluoroethylene (PTFE), polyolefins, polyalkylenes, polyethers, styrene-butadiene, copolymers of polysiloxanes and polysiloxanes, branched polyethers, polyvinyl ethers, copolymers thereof and/or additions thereof. The binder may include a cellulose, such as carboxymethyl cellulose (CMC). In some embodiments, the polyolefin may include Polyethylene (PE), polypropylene (PP), polyvinylidene fluoride (PVDF), copolymers thereof, and/or blends thereof. For example, the binder may include polyvinyl chloride, polyphenylene oxide (PPO), polyethylene-block-poly (ethylene glycol), poly (ethylene oxide) (PEO), polyphenylene oxide (PPO), polyethylene-block-poly (ethylene glycol), Polydimethylsiloxane (PDMS), polydimethylsiloxane-alkylmethylsiloxane, copolymers thereof, and/or mixtures thereof. In some embodiments, the adhesive comprises a fibrillatable polymer. In certain embodiments, the binder comprises, consists essentially of, or consists of PTFE.
In some embodiments, the binder may include PTFE and optionally one or more additional binder components. In some embodiments, the binder may include one or more polyolefins and/or copolymers thereof and PTFE. In some embodiments, the binder may comprise PTFE and one or more of cellulose, polyolefin, polyether precursor, polysiloxane, copolymers thereof, and/or additions thereof. The addition of the polymer may include an interpenetrating network of the above-mentioned polymers or copolymers.
The adhesive may include various suitable proportions of the polymer components. For example, the PTFE may be up to about 100% by weight of the binder, such as from about 20% to about 95%, from about 20% to about 90%, including: from about 20 wt% to about 80 wt%, from about 30 wt% to about 70 wt%, from about 30 wt% to about 50 wt%, or from about 50 wt% to about 90 wt%. In further embodiments, the binder may include PTFE, CMC, and PVDF as the binder. In certain embodiments, the electrode film may include 2 wt.% PTFE, 1 wt.% CMC, and 1 wt.% PVDF. For example, the binder mixture may include a mass of PTFE that is 50% of the total binder content of the electrode film and 2% of the total mass of the electrode film.
In some embodiments, the electrode film mixture may include binder particles having a selected size. In some embodiments, the binder particles may be about 50nm, about 100nm, about 150nm, about 200nm, about 250nm, about 300nm, about 350nm, about 400nm, about 450nm, about 500nm, about 1 μm, about 2 μm, about 3 μm, about 4 μm, about 5 μm, about 10 μm, about 50 μm, about 100 μm, or any range therebetween.
As used herein, the dry manufacturing process may refer to a process that does not use or substantially does not use a solvent in the formation of the electrode film. For example, the components of the active layer or electrode film, including the carbon material and binder, may include dry particles. The dry particles used to form the active layer or electrode film can be combined to provide a dry particle active layer mixture. In some embodiments, the active layer or electrode film may be formed from a dry particulate active layer mixture such that the weight percentages of the components of the active layer or electrode film are substantially the same as the weight percentages of the components of the dry particulate active layer mixture. In some embodiments, an active layer or electrode film formed from a dry particulate active layer mixture using a dry manufacturing process may be free or substantially free of any processing additives, such as solvents and solvent residues resulting therefrom. In some embodiments, the resulting active layer or electrode film is a self-supporting film formed from a dry particle mixture using a dry process. In some embodiments, the resulting active layer or electrode film is a free-standing film formed from a dry particle mixture using a dry process. The process of forming the active layer or electrode film may include fibrillating the fibrillatable binder component such that the film includes a fibrillated binder. In further embodiments, a free-standing active layer or electrode film may be formed without a current collector. In still further embodiments, the active layer or electrode film may include a fibrillated polymer matrix such that the film is self-supporting. It is believed that a matrix, lattice or network of fibrils may be formed to provide a mechanical structure for the electrode film.
In some embodiments, an energy storage device electrode film (where the electrode film is a dry and/or self-supporting film) may provide a material loading or active material loading (which may be expressed as a mass per unit area of the electrode film or current collector) as follows: about 12mg/cm2About 13mg/cm2About 14mg/cm2About 15mg/cm2About 16mg/cm2About 17mg/cm2About 18mg/cm2About 19mg/cm2About 20mg/cm2About 21mg/cm2About 22mg/cm2About 23mg/cm2About 24mg/cm2About 25mg/cm2About 26mg/cm2About 27mg/cm2About 28mg/cm2About 29mg/cm2About 30mg/cm2About 50mg/cm2Or about 60mg/cm2Or about 70mg/cm2Or about 80mg/cm2Or about 90mg/cm2Or about 100mg/cm2Or any range of values therebetween.
In some embodiments, an energy storage device electrode film (where the electrode film is a dry and/or self-supporting film) can provide a specific capacity (which can be expressed as a capacity per unit mass of active material) as follows: about 100mAh/g, about 125mAh/g, about 150mAh/g, about 160mAh/g, about 170mAh/g, about 175mAh/g, about 176mAh/g, about 177mAh/g, about 179mAh/g, about 180mAh/g, about 185mAh/g, about 190mAh/g, about 196mAh/g, about 200mAh/g, about 250mAh/g, about 300mAh/g, about 350mAh/g, about 354mAh/g, or about 400mAh/g, or any range of values therebetween. In further embodiments, the energy storage device electrode film (where the electrode film is a dry and/or self-supporting film) may provide a specific capacity (which may be expressed as a capacity per unit mass of the electrode film or current collector) of at least about 100mAh/g, or at least about 150mAh/g, any range of values therebetween. In some embodiments, the specific capacity is a charge capacity. In a further embodiment, the specific capacity is the discharge capacity. In some embodiments, the electrode may be a negative electrode and/or a positive electrode. In some embodiments, the specific capacity may be the first charge and/or discharge capacity. In further embodiments, the specific capacity may be a charge and/or discharge capacity measured after the first charge and/or discharge.
In some embodiments, the self-supporting dry electrode films described herein may advantageously exhibit improved performance relative to typical electrode films. The property may be, for example, tensile strength, elasticity (elongation), bendability, coulombic efficiency, capacity, or electrical conductivity. In some embodiments, the energy storage device electrode film (where the electrode film is a dry and/or free standing film) can provide coulombic efficiency, e.g.,
In some embodiments, an energy storage device electrode film or electrode (where the electrode film is or includes a dry and/or self-supporting film) may provide a capacity retention percentage (which may be represented by a charge or discharge capacity at a given rate divided by a charge or discharge capacity measured at C/10) as follows: about or at least about 10%, about or at least about 20%, about or at least about 30%, about or at least about 40%, about or at least about 50%, about or at least about 60%, about or at least about 70%, about or at least about 80%, about or at least about 90%, about or at least about 98%, about or at least about 99%, about or at least about 99.9%, or about or at least about 100%, or any range therebetween. In some embodiments, the charge or discharge rate for the capacity retention percentage is at or at least C/10, C/5, C/3(0.33C), C/2, 1C, 1.5C, or 2C, or any range of values therebetween. The charge or discharge rate of the capacity retention percentage may be measured at a set number of charge and discharge cycles after the first charge or discharge cycle. In some embodiments, the charge or discharge rate of the capacity retention percentage is measured as 1, 5, 10, 50, 100, 200, 300, 400, 500, 600, 700, or 1000 cycles, or any range of values therebetween.
In some embodiments, the self-supporting dry electrode films described herein may advantageously exhibit improved performance relative to typical electrode films. The property may be, for example, coulombic efficiency, capacity, or conductivity.
In the following specific examples, energy storage devices including the electrolyte formulations described herein were fabricated.
Examples of the invention
Example 1
The study shown in example 1 examined the results of the tests consisting primarily of EC, EMC, DMC, PC and LiPF6Electrolyte formulations of composition (see table 1) and the effect of electrode material, electrode formulation, dry electrode process on electrochemical performance in half cells as well as full cell configurations are characterized. It was found that the proportion of EMC or DMC in each EC-based electrolyte solution partially determines the electrochemical performance of the negative electrode. For example, EMC-rich and EC-based electrolyte formulation solvents for spheroidal graphite compositions were found to have improved capacity at high discharge rates. Furthermore, it was found that EC-based and DMC-rich electrolyte solvents will also exhibit improved capacity at high discharge C-rates when used with shaped graphite compositions.
The following 6 solvent formulations were developed and evaluated with dry processed battery electrodes made from different active materials and electrode processing conditions to better enhance overall electrochemical performance. This improvement balances the compatibility of the resulting electrolyte candidate with the designed dry cell electrode and prevents undesirable reactions of the electrolyte on the dry electrode surface:
an EC-based solvent mixture comprising one or more solvents.
An EC-based solvent mixture comprising one or more solvents wherein the EMC is higher than typical ratios.
An EC-based solvent mixture comprising one or more solvents wherein DMC is higher than a typical ratio.
A solvent mixture based on EC comprising one or more solvents wherein DEC is higher than typical ratio.
A solvent mixture based on EC comprising one or more solvents with a PC higher than the typical ratio.
An EC-based solvent mixture comprising one or more solvents with the same ratio of solvents to one another.
Commercial nonaqueous solvents including EC, EMC, DEC, DMC, PC, EA and blends thereof were used in various combinations and without further purification. The solvent volume ratios formulated as detailed below with respect to the formulation examples are provided in table 1.
TABLE 1 electrolyte formulations with different solvent ratios examined in preliminary experiments
EC
EMC
DMC
PC
Preparation
1
1
2
0.1
0.02
LiPF6
Preparation 2
1
0
3
0
LiPF6
Preparation 3
1
2.4
0
0
LiPF6
Preparation 4
1
0.5
3
0
LiPF6
Preparation 5
1
1
1
0
LiPF6
Preparation 6
1
4
0
0
LiPF6
Preparation 7
1
0
4
0
LiPF6
The resulting electrolyte formulations were evaluated in single layer dry electrode half cells and full cells to evaluate the effect of solvent formulations on electrode performance. The electrochemical performance of the cell was measured by a galvanostatic charging step followed by a potentiostatic step and discharged at room temperature in the galvanostatic step.
Electrolyte formulation candidates were benchmarked using thick dry electrodes as they provided greater sensitivity to overall performance due to the fact thatCracking, delamination, rigidity, etc., subject to the limitations of wet coating techniques. The preliminary experiments disclosed herein used about 23mg/cm2And about 45mg/cm of dry negative electrode2Electrode loading of dry positive electrode(s).
Fig. 3A shows the capacity of the natural graphite based negative half-cell in the case of
Fig. 4A and 4B show the charge and discharge capacities of surface modified artificial graphite negative half-cells prepared using two different electrode formulations (
TABLE 2
Fig. 5 also shows the charge and discharge capacity of the surface modified artificial graphite anode half-cell prepared using the third electrode formulation with multiple electrolyte solvent systems (process 3). Fig. 5 shows:
TABLE 3
Fig. 6A shows the capacity of the flake artificial graphite negative electrode half-cell in the case of
Fig. 7A shows the capacity of formulations 1-5, and fig. 7B shows the coulombic efficiency, for use in a full cell consisting of layered lithium nickel manganese cobalt oxide (NMC) as the dry positive electrode and surface modified artificial graphite as the dry negative electrode. Fig. 7A and 7B show:
Example 2
In example 2, the electrochemical performance of NMC positive and surface modified artificial graphite (SMG-a5) negative full cells (NMC/Gr) incorporating
Fig. 8A shows the capacity of NMC 811/Gr full cells, fig. 8B shows the capacity of NMC622/Gr full cells, and fig. 8C shows the efficiency of NMC 811/Gr and NMC622/Gr full cells filled with the electrolytes of
TABLE 4 electrode and electrolyte specifications
Electrolyte
Positive electrode
Loading
Negative Loading
Preparation
1
NMC811
40mg/cm2
Gr
23.5mg/cm2
Preparation 3
NMC811
39.9mg/cm2
Gr
23.6mg/cm2
Preparation 1
NMC622
39.5mg/cm2
Gr
20.5mg/cm2
Preparation 3
NMC622
39.9mg/cm2
Gr
20.7mg/cm2
The performance of NMC 811/Gr full cells with
Fig. 9A shows NMC622/Gr full cell discharge capacity retention with
TABLE 5 average Charge Capacity maintenance at different rates for NMC622/Gr full cells with
Rate of speed
1C
2C
3C
4C
5C
Charging of electricity
94.2％
60.3％
53.5％
51.3％
50.6％
Fig. 10A shows NMC622/Gr full cell discharge capacity retention with
TABLE 6 average Charge Capacity maintenance at different rates for NMC622/Gr full cells with
Rate of speed
1C
2C
3C
4C
5C
Charging of electricity
94.5％
68.1％
60.8％
58.7％
57.6％
Fig. 9A to 10B and tables 5 and 6 show that
While certain embodiments of the present invention have been described, these embodiments have been presented by way of example only, and are not intended to limit the scope of the disclosure. Indeed, the novel methods and systems described herein may be embodied in a variety of other forms. Furthermore, various omissions, substitutions and changes in the systems and methods described herein may be made without departing from the spirit of the disclosure. The accompanying claims and their equivalents are intended to cover such forms or modifications as would fall within the scope and spirit of the disclosure. Accordingly, the scope of the invention is to be defined only by reference to the following claims.
Features, materials, characteristics or groups described in connection with a particular aspect, embodiment or example should be understood to apply to any other aspect, embodiment or example described in this section or elsewhere in this specification, unless incompatible therewith. All of the features disclosed in this specification (including any accompanying claims, abstract and drawings), and/or all of the steps of any method or process so disclosed, may be combined in any combination, except combinations where at least some of such features and/or steps are mutually exclusive. The protection is not restricted to the details of any of the foregoing embodiments. This protection extends to any novel one, or any novel combination, of the features disclosed in this specification (including any accompanying claims, abstract and drawings), or to any novel one, or any novel combination, of the steps of any method or process so disclosed.
Furthermore, certain features that are described in this disclosure in the context of separate implementations can also be implemented in combination in a single implementation. Conversely, various features that are described in the context of a single implementation can also be implemented in multiple implementations separately or in any suitable subcombination. Furthermore, although features may be described above as acting in certain combinations, one or more features from a claimed combination can in some cases be excised from the combination, and the combination may be claimed as a subcombination or variation of a subcombination.
Further, while operations may be depicted in the drawings or described in the specification in a particular order, such operations need not be performed in the particular order shown or in sequential order, or all of the operations need not be performed, to achieve desirable results. Other operations not depicted or described may be incorporated into the example methods and processes. For example, one or more additional operations may be performed before, after, concurrently with, or between any of the operations described. Further, in other implementations, the operations may be rearranged or reordered. Those skilled in the art will appreciate that in some embodiments, the actual steps taken in the processes shown and/or disclosed may differ from those shown in the figures. Depending on the embodiment, some of the steps described above may be removed, and other steps may be added. Furthermore, the features and attributes of the specific embodiments disclosed above can be combined in different ways to form additional embodiments, all of which fall within the scope of the present disclosure. Moreover, the separation of various system components in the implementations described above should not be understood as requiring such separation in all implementations, and it should be understood that the described components and systems can generally be integrated together in a single product or packaged into multiple products. For example, any of the components described herein for an energy storage system may be provided separately, or integrated together (e.g., packaged together, or attached together) to form an energy storage system.
For the purposes of this disclosure, certain aspects, advantages, and novel features are described herein. Not all of these advantages may be achieved in accordance with any particular embodiment. Thus, for example, those skilled in the art will recognize that the invention may be embodied or carried out in a manner that achieves one advantage or group of advantages as taught herein without necessarily achieving other advantages as may be taught or suggested herein.
Unless specifically stated otherwise, or otherwise understood in the context of use, conditional languages such as "may", "can", "may" are generally intended to convey that certain embodiments include, while other embodiments do not include, certain features, elements and/or steps. Thus, such conditional language is not generally intended to imply that features, elements and/or steps are in any way required for one or more embodiments or that one or more embodiments necessarily include logic for deciding, with or without user input or prompting, whether such features, elements and/or steps are included or are to be performed in any particular embodiment.
A conjunctive such as the phrase "X, Y and at least one of Z," unless specifically stated otherwise, in connection with the context, is understood to be commonly used to express items, terms, etc. as either of X, Y and Z. Thus, such conjunctions are not generally intended to imply that certain embodiments require the presence of at least one of X, at least one of Y, and at least one of Z.
The terms "approximate," "about," "generally," "substantially," and the like as used herein mean a value, amount, or characteristic that is close to the stated value, amount, or characteristic, yet still performs the desired function or achieves the desired result. For example, the terms "approximately," "about," "generally," "substantially," and "approximately" can refer to an amount within less than 10%, within less than 5%, within less than 1%, within less than 0.1%, and within less than 0.01% of the stated amount, depending on the desired function or desired result.
The scope of the present disclosure is not intended to be limited by the particular disclosure of the preferred embodiments in this section or elsewhere in this specification, and may be defined by the claims set forth in this section or elsewhere in this specification or set forth in the future. The language of the claims is to be construed broadly based on the language used in the claims and not limited to examples described in the specification or during the prosecution of the application, which examples are to be construed as non-exclusive.
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