System and method for pre-forming catholyte interface on cathode active material

Abstract

A method for pre-forming a catholyte interface on an electroactive material, the method comprising providing a current or voltage to an electrochemical reactor comprising a cation source, an electrolyte mixture, one or more additives, and a catholyte active material in contact with one another, wherein the current or voltage is used to ionize and form cations at the cation source that react with the cathode active material to pre-form a catholyte interface on the cathode active material.

Description

[0001] Government funding

[0002] This invention was developed with government support under the Department of Energy protocol number DE-AC02-06CH11357 Ex Situ Lithiation for Li-Ion Battery Anodes. The government may hold certain rights to this invention. Technical Field

[0003] This invention relates generally to electroactive materials, and more specifically to preformed cathode electrolyte interfaces for electrochemical batteries, and methods of manufacturing and using the same. Background Technology

[0004] The information provided in this section is intended to provide a general overview of the background of this disclosure. To the extent described in this section, the work of the currently named inventors, and aspects of the description that may not conform to the prior art at the time of submission, are neither explicitly nor implicitly acknowledged as prior art relative to this disclosure.

[0005] Advanced energy storage devices and systems are needed to meet the energy and / or power requirements of various products, including automotive products such as start-stop systems (e.g., 12V start-stop systems), battery auxiliary systems, hybrid electric vehicles (“HEVs”), and electric vehicles (“EVs”). A typical battery includes at least two electrodes and an electrolyte and / or a separator. One of the two electrodes can be used as the positive electrode or cathode, and the other as the negative electrode or anode. A separator filled with a liquid, solid, or semi-solid electrolyte can be disposed between the negative and positive electrodes. The electrolyte is adapted to conduct ions (e.g., lithium ions, calcium ions, sodium ions, and / or potassium ions) between the electrodes and, like the two electrodes, can be in solid and / or liquid form and / or a mixture thereof. In the case of solid-state batteries, which include solid electrodes and a solid electrolyte (or solid separator), the solid electrolyte (or solid separator) can physically separate the electrodes, thus eliminating the need for a separate separator.

[0006] Traditional rechargeable batteries operate by reversibly transferring ions back and forth between the negative and positive electrodes. For example, during battery charging, ions can move from the positive electrode to the negative electrode, and vice versa during battery discharge. Such batteries can reversibly supply power to a relevant load device as needed. More specifically, the battery can supply electrical energy to the load device until the lithium, calcium, sodium, and / or potassium content at the negative electrode is effectively depleted. The battery can then be recharged by transferring a suitable direct current in the opposite direction between the electrodes.

[0007] During discharge, the negative electrode may contain a relatively high concentration of intercalated lithium, calcium, sodium, and / or potassium, which are oxidized to lithium ions, calcium ions, sodium ions, and / or potassium ions, releasing electrons. Lithium ions, calcium ions, sodium ions, and / or potassium ions can move from the negative electrode to the positive electrode, for example, through an ion-conducting electrolyte solution contained within the pores of an inserted porous separator. Simultaneously, electrons flow from the negative electrode to the positive electrode through an external circuit. Such lithium ions, calcium ions, sodium ions, and / or potassium ions can be absorbed into the material of the positive electrode through an electrochemical reduction reaction. The battery can be partially or fully discharged to its usable capacity using an external power source and then recharged or regenerated, reversing the electrochemical reactions that occurred during discharge. Summary of the Invention

[0008] In one configuration, a method for pre-forming a cathode electrolyte interface on an electroactive material is provided. The method includes supplying a current or voltage to an electrochemical reactor comprising a cation source, an electrolyte mixture, one or more additives in contact with each other, and a cathode active material, wherein the current or voltage is used to ionize and form cations at the cation source, which react with the cathode active material to pre-form a cathode electrolyte interface on the cathode active material.

[0009] The method may include one or more of the following optional aspects or steps. For example, the electrolyte mixture may include a cathode active material, and the method further includes preparing the electrolyte mixture by contacting the cathode active material with the electrolyte prior to placement in an electrochemical reactor, wherein the electrolyte mixture may include greater than or equal to about 1 gram of cathode active material / 20 mL of electrolyte. The cathode active material may be a positive electrode material.

[0010] According to at least one aspect, the cathode active material may include materials selected from: lithium nickel manganese cobalt oxide, lithium-rich manganese base oxide or lithium manganese oxide and any combination thereof.

[0011] According to another perspective, the cation source may include cations selected from lithium, calcium, sodium, potassium, and any combination thereof.

[0012] According to at least one example, one or more additives may include materials selected from lithium salt molecules, fluorinated organic molecules, or organometallic molecules.

[0013] According to another example, current or voltage can be supplied for a period of time greater than or equal to about 5 hours to less than or equal to about 100 hours.

[0014] According to at least one aspect, the current or voltage may include a first current or voltage, which may be provided during a first time period, and the method may further include providing a second current or voltage during a second time period, wherein the second current or voltage is different from the first current or voltage.

[0015] According to another aspect, the method may further include one or more filtration steps, one or more rinsing steps, or a combination of one or more filtration steps and one or more rinsing steps to collect electroactive material from the electrolyte mixture.

[0016] According to at least one example, the method may also include one or more constant current or constant potential steps.

[0017] In another configuration, a method for forming an electroactive material is provided. The method includes contacting a cathode active material with an electrolyte in an electrochemical reactor, the electrochemical reactor further including a cation source comprising cations selected from lithium, calcium, sodium, potassium, and combinations thereof, the electrolyte having a temperature greater than or equal to about 25°C and less than or equal to about 150°C. The method further includes supplying a current or voltage to the cation source in contact with the electrolyte in the electrochemical reactor to ionize and form cations, which are then reduced onto the cathode active material to form the electroactive material.

[0018] The method may include one or more of the following optional aspects or steps. For example, the electrolyte may include greater than or equal to about 1 gram of cathode active material per 20 milliliters of electrolyte.

[0019] According to at least one aspect, the cathode active material may include positively active materials selected from: lithium nickel manganese cobalt oxide, lithium-rich manganese base oxide or lithium manganese oxide and any combination thereof.

[0020] On the other hand, the current can be greater than or equal to approximately 0.1 mA / cm. 2 to less than or equal to approximately 25 mA / cm 2 It is provided in an electrochemical reactor.

[0021] According to at least one example, one or more additives may be added to an electrochemical reactor, the additives including materials selected from lithium salt-based molecules, fluorinated organic molecules, or organometallic-based molecules.

[0022] According to another example, the current or voltage can be provided for a period of time greater than or equal to about 5 hours or less than or equal to about 100 hours.

[0023] According to at least one aspect, the current or voltage can be a first current or voltage, the first current or voltage can be provided in a first time period, and the method can further include providing a second current or voltage in a second time period, wherein the second current or voltage can be different from the first current or voltage.

[0024] According to another aspect, the method may also include one or more constant current or constant potential steps.

[0025] In yet another configuration, a method for forming an electroactive material is provided. The method includes contacting a cathode active material with an electrolyte in an electrochemical reactor, the electrochemical reactor further including a cation source and one or more additives. The method also includes supplying a current or voltage to the cation source in contact with the electrolyte in the electrochemical reactor at a first current or voltage during a first time period, and supplying a second current or voltage during a second time period, the second current or voltage being different from the first current or voltage.

[0026] The method may include one or more of the following optional aspects or steps. For example, the first and second time periods may be greater than or equal to about 5 hours, or less than or equal to about 100 hours. Attached Figure Description

[0027] The accompanying drawings described herein are for illustrative purposes only and are not intended to limit the scope of this disclosure.

[0028] Figure 1 This is a diagram of an example electrochemical cell;

[0029] Figure 2 This is a diagram of an example electrochemical reactor for non-in-situ electrochemical pre-formation of a cathode electrolyte interface on an electroactive material, based on the principles of this disclosure.

[0030] Figure 3A This is a flowchart illustrating an example method for pre-forming a cathode electrolyte interface onto electroactive cathode material particles according to various aspects of this disclosure;

[0031] Figure 3B This is a flowchart illustrating an example method for pre-forming a cathode electrolyte interface onto electroactive cathode material particles according to various aspects of this disclosure;

[0032] Figure 3C This is a flowchart illustrating an example method for pre-forming a cathode electrolyte interface onto electroactive cathode material particles according to various aspects of this disclosure;

[0033] Figure 4A and 4B This is a schematic diagram of a potential-constant method for pre-forming a cathode electrolyte interface onto electroactive cathode material particles; and

[0034] Figure 5A and 5B This is a schematic diagram of a current-driven method for pre-forming a cathode electrolyte interface onto electroactive cathode material particles.

[0035] In all the accompanying drawings, the corresponding reference numerals indicate the corresponding parts. Detailed Implementation

[0036] The example configuration will now be described more fully with reference to the accompanying drawings. The example configuration is provided so that this disclosure will be thorough and will fully communicate the scope of this disclosure to those skilled in the art. Specific details, such as examples of specific components, devices, and methods, are set forth to provide a thorough understanding of the configuration of this disclosure. It will be apparent to those skilled in the art that the specific details are not required, that the example configuration may be implemented in many different forms, and that the specific details and exemplary configuration should not be construed as limiting the scope of this disclosure.

[0037] The terminology used herein is for the purpose of describing specific exemplary configurations only and is not intended to be limiting. As used herein, the singular articles “a,” “an,” and “the” may also be intended to include plural forms unless the context clearly indicates otherwise. The terms “comprising,” “including,” “containing,” and “having” are inclusive, thus specifying the presence of features, steps, operations, elements, and / or components, but not excluding the presence or addition of one or more other features, steps, operations, elements, components, and / or groups thereof. The method steps, processes, and operations described herein should not be construed as requiring them to be performed in the specific order discussed or shown, unless specifically identified as such. Additional or alternative steps may be employed.

[0038] When an element or layer is referred to as “on another element or layer,” “joined to,” “connected to,” “attached to,” or “linked to” another element or layer, it may be directly on, joined to, connected to, attached to, or linked to the other element or layer, or there may be intermediate elements or layers present. Conversely, when an element is referred to as “directly on another element or layer,” “directly joined to,” “directly connected to,” “directly attached to,” or “directly linked to” another element or layer, there may be no intermediate elements or layers present. Other terms used to describe relationships between elements should be interpreted in a similar manner (e.g., “between” vs. “directly between,” “adjacent” vs. “directly adjacent,” etc.). As used herein, the term “and / or” includes any and all combinations of one or more of the related listed items.

[0039] The terms first, second, third, etc., may be used herein to describe various elements, components, regions, layers, and / or parts. These elements, components, regions, layers, and / or parts should not be limited by these terms. These terms are used only to distinguish individual elements, components, regions, layers, or parts. Terms such as “first,” “second,” and other numerical terms do not imply order or sequence unless the context clearly indicates otherwise. Therefore, the first element, component, region, layer, or part discussed below may be referred to as the second element, component, region, layer, or part without departing from the teachings of the example configuration.

[0040] In this application, including the following definitions, the term "module" may be replaced by the term "circuit". The term "module" may refer to or be a part of an application-specific integrated circuit (ASIC), or include ASICs; digital, analog, or mixed-signal analog / digital discrete circuits; digital, analog, or mixed-signal analog / digital integrated circuits; combinational logic circuits; field-programmable gate arrays (FPGAs); processors (shared, dedicated, or grouped) that execute code; memory (shared, dedicated, or grouped) that stores code executed by the processor; other suitable hardware components that provide the functions described; or some or all of the above, such as in a system-on-a-chip.

[0041] The term "code" as used above can include software, firmware, and / or microcode, and can refer to programs, routines, functions, classes, and / or objects. The term "shared processor" includes a single processor that executes some or all of the code from multiple modules. The term "group processor" includes a processor, in conjunction with an additional processor, that executes some or all of the code from one or more modules. The term "shared memory" includes a single memory that stores some or all of the code from multiple modules. The term "group memory" includes memory, in conjunction with additional memory, that stores some or all of the code from one or more modules. The term "memory" can be a subset of the term "computer-readable medium." The term "computer-readable medium" does not include transient electrical and electromagnetic signals propagating through the medium and can therefore be considered tangible, non-transitory memory. Non-limiting examples of non-transitory memory include tangible computer-readable media, including non-volatile memory, magnetic memory, and optical memory.

[0042] The apparatus and methods described in this application may be implemented, in whole or in part, by one or more computer programs executed by one or more processors. The computer program includes processor-executable instructions stored on at least one non-transitory tangible computer-readable medium. The computer program may also include and / or depend on stored data.

[0043] A software application (i.e., a software resource) can refer to computer software that enables a computing device to perform tasks. In some examples, a software application may be referred to as an "application," "app," or "program." Example applications include, but are not limited to, system diagnostic applications, system management applications, system maintenance applications, word processing applications, spreadsheet applications, messaging applications, media streaming applications, social networking applications, and game applications.

[0044] Non-transitory memory can be a physical device used for temporary or permanent storage of programs (e.g., instruction sequences) or data (e.g., program state information) for use by a computing device. Non-transitory memory can be volatile and / or non-volatile addressable semiconductor memory. Examples of non-volatile memory include, but are not limited to, flash memory and read-only memory (ROM) / programmable read-only memory (PROM) / erasable programmable read-only memory (EPROM) / electrically erasable programmable read-only memory (EEPROM) (e.g., commonly used in firmware, such as bootloaders). Examples of volatile memory include, but are not limited to, random access memory (RAM), dynamic random access memory (DRAM), static random access memory (SRAM), phase-change memory (PCM), and magnetic disks or magnetic tapes.

[0045] These computer programs (also referred to as programs, software, software applications, or code) include machine instructions for a programmable processor and can be implemented using high-level procedural and / or object-oriented programming languages ​​and / or assembly / machine languages. As used herein, the terms "machine-readable medium" and "computer-readable medium" refer to any computer program product, non-transitory computer-readable medium, apparatus, and / or device (e.g., disk, optical disk, memory, programmable logic device (PLD)) used to provide machine instructions and / or data to a programmable processor, including machine-readable media that receive machine instructions as machine-readable signals. The term "machine-readable signal" refers to any signal used to provide machine instructions and / or data to a programmable processor.

[0046] Various implementations of the systems and techniques described herein can be implemented in digital electronic and / or optical circuits, integrated circuits, specially designed ASICs (Application-Specific Integrated Circuits), computer hardware, firmware, software, and / or combinations thereof. These different implementations may include implementations in one or more computer programs executable and / or interpretable on a programmable system, the programmable system including at least one programmable processor, at least one input device, and at least one output device, the programmable processor being dedicated or general-purpose, coupled to receive data and instructions from and send data and instructions to the storage system.

[0047] The processes and logic flows described in this specification can be executed by one or more programmable processors, also known as data processing hardware, which execute one or more computer programs to perform functions by manipulating input data and generating output. These processes and logic flows can also be executed by special-purpose logic circuits, such as FPGAs (Field-Programmable Gate Arrays) or ASICs (Application-Specific Integrated Circuits). For example, processors suitable for executing computer programs include general-purpose and special-purpose microprocessors, as well as any one or more processors of any kind of digital computer. Typically, the processor receives instructions and data from read-only memory or random access memory, or both. The basic components of a computer are a processor for executing instructions and one or more storage devices for storing instructions and data. Typically, a computer will also include or be operatively coupled to one or more mass storage devices for storing data, such as magnetic disks, magneto-optical disks, or optical disks, to receive data from or transfer data to, or both. However, a computer does not need to have such devices. Computer-readable media suitable for storing computer program instructions and data include all forms of non-volatile memory, media, and storage devices, including, for example, semiconductor storage devices such as EPROM, EEPROM, and flash memory devices; magnetic disks such as internal hard disks or removable disks; magneto-optical disks; and CD-ROMs and DVD-ROMs. Processors and memory may be supplemented or incorporated therein by dedicated logic circuitry.

[0048] To provide interaction with the user, one or more aspects of this disclosure can be implemented on a computer having a display device for displaying information to the user, such as a CRT (cathode ray tube), LCD (liquid crystal display) monitor, or touchscreen, and optional keyboard and pointing device, such as a mouse or trackball, through which the user can provide input to the computer. Other types of devices can also be used to provide interaction with the user; for example, feedback provided to the user can be any form of sensory feedback, such as visual, auditory, or tactile feedback; and input from the user can be received in any form, including sound, speech, or tactile input. Furthermore, the computer can interact with the user by sending documents to and receiving documents from the device used by the user; for example, by sending a webpage to a web browser on the user's client device in response to a request received from a web browser.

[0049] The principles of this disclosure relate to electroactive materials, and more specifically, to electroactive materials having a pre-formed cathode electrolyte interface (CEI) for use in electrochemical batteries, and methods for their manufacture and use. For example, this disclosure provides a method for pre-forming a cathode electrolyte interface on an electroactive material to mitigate low first-cycle coulombic efficiency (CE) (i.e., lithium is no longer consumed by CEI formation during the first cycle). As discussed in more detail below, the introduction of additives can induce the formation of certain CEI components and structures (e.g., thickness) that affect properties and performance.

[0050] As background, Figure 1 An exemplary schematic diagram of an electrochemical battery (also known as a battery pack) 20 is shown. While the following discussion pertains to lithium-ion electrochemical batteries that cycle lithium ions, it should be understood that similar teachings apply to calcium-ion electrochemical batteries that cycle calcium ions, sodium-ion electrochemical batteries that cycle sodium ions, and / or potassium-ion electrochemical batteries that cycle potassium ions. In each case, the electrochemical battery can be used in vehicle or automotive transportation applications (e.g., motorcycles, boats, tractors, buses, motorbikes, mobile homes, campers, and tanks). Electrochemical batteries can also be used in a wide variety of other industrial and applications, including aerospace components, consumer products, devices, buildings (e.g., houses, offices, sheds, and warehouses), office equipment and furniture, as well as industrial equipment machinery, agricultural or farm equipment, or heavy machinery, as non-limiting examples. Furthermore, although the examples shown include a single positive electrode cathode and a single anode, it should be recognized that this teaching extends to a variety of other configurations, including configurations having one or more cathodes and one or more anodes, and various current collectors having electroactive layers disposed on or adjacent to one or more of their surfaces.

[0051] Continue to refer to Figure 1The battery 20 includes a negative electrode 22 (e.g., an anode), a positive electrode 24 (e.g., a cathode), and a separator 26 disposed between the two electrodes 22, 24. The separator 26 provides electrical isolation between the electrodes 22, 24—preventing physical contact. During lithium-ion cycling, the separator 26 also provides a path of least resistance for the internal passage of lithium ions and, in some cases, associated anions. Like the negative electrode 22 and / or the positive electrode 24, the separator 26 can be in solid and / or liquid form and / or a mixture thereof. For example, in some variations, the separator 26 may include an electrolyte 30, which may also be present in the negative electrode 22 and / or the positive electrode 24. In some variations, the separator 26 may be formed of a solid electrolyte or a semi-solid electrolyte (e.g., a gel electrolyte). For example, the separator 26 may include multiple solid electrolyte particles and / or gel electrodes. The negative electrode 22 and / or the positive electrode 24 may additionally or alternatively include multiple solid electrolyte particles and / or gel electrolytes. The solid electrolyte particles and / or gel electrolyte contained in or defining the separator 26 may be the same as or different from the solid electrolyte particles and / or gel electrolyte contained in the positive electrode 24 and / or negative electrode 22, and the solid electrolyte particles and / or gel electrolyte contained in the positive electrode 24 may be the same as or different from the solid electrolyte particles and / or gel electrolyte contained in the negative electrode 22.

[0052] A first current collector 32 (e.g., a negative current collector) may be located at or near the negative electrode (also referred to as a negatively charged active material layer) 22. The first current collector 32, together with the negative electrode 22, may be referred to as a negative electrode assembly. Although not shown, those skilled in the art will understand that in some variations, the negatively charged active material layer 22 may be disposed on one or more parallel sides of the first current collector 32. Similarly, those skilled in the art will understand that in other variations, the negatively charged active material layer 22 may be disposed on a first side of the first current collector 32, and the positively charged active material layer 24 may be disposed on a second side of the first current collector 32. In each case, the first current collector 32 may be a metal foil, a metal grid, or a screen, or an expanded metal comprising copper or any other suitable conductive material known to those skilled in the art.

[0053] The second current collector 34 (e.g., a positive current collector) may be located at or near the positive electrode (also referred to as the positively charged active material layer) 24. The second current collector 34, together with the positive electrode 24, may be referred to as the positive electrode assembly. Although not shown, those skilled in the art will understand that in some variations, the positively charged active material layer 24 may be disposed on one or more parallel sides of the second current collector 34. Similarly, those skilled in the art will understand that in other variations, the positively charged active material layer 24 may be disposed on a first side of the second current collector 34, and the negatively charged active material layer 22 may be disposed on a second side of the second current collector 34. In each case, the second electrode current collector 34 may be a metal foil, a metal mesh, or a sieve, or an expanded metal comprising aluminum or any other suitable conductive material known to those skilled in the art.

[0054] The first current collector 32 and the second current collector 34 can respectively collect free electrons and move them to and from the external circuit 40. For example, the interruptible external circuit 40 and the load device 42 can be connected to the negative electrode 22 (via the first current collector 32) and the positive electrode 24 (via the second current collector 34). The battery 20 can generate current during discharge through a reversible electrochemical reaction that occurs when the external circuit 40 is closed (to connect the negative electrode 22 and the positive electrode 24) and the negative electrode 22 has a lower potential than the positive electrode. The chemical potential difference between the positive electrode 24 and the negative electrode 22 drives electrons generated by the reaction at the negative electrode 22 (e.g., the oxidation of intercalated lithium) to move through the external circuit 40 toward the positive electrode 24. Lithium ions generated at the negative electrode 22 are simultaneously transferred toward the positive electrode 24 through the electrolyte 30 contained in the separator 26. Electrons flow through the external circuit 40, and lithium ions migrate through the separator 26 containing the electrolyte 30 to form intercalated lithium at the positive electrode 24. As described above, the electrolyte 30 is also typically present in the negative electrode 22 and the positive electrode 24. The current passing through the external circuit 40 can be utilized and guided through the load device 42 until the lithium in the negative electrode 22 is depleted and the capacity of the battery 20 decreases.

[0055] By connecting an external power source to the lithium-ion battery 20 to reverse the electrochemical reactions that occur during battery discharge, the battery 20 can be charged or recharged at any time. Connecting an external electrical energy source to the battery 20 facilitates reactions, such as the non-spontaneous oxidation of lithium intercalated at the positive electrode 24, generating electrons and lithium ions. The lithium ions flow back through the separator 26 and electrolyte 30 to the negative electrode 22 to replenish it with lithium (e.g., intercalated lithium) for use during the next battery discharge event. Thus, a cycle is considered to be a full discharge followed by a full charge event, in which lithium ions circulate between the positive and negative electrodes 24. The external power source that can be used to charge the battery 20 can vary depending on the size, construction, and specific end use of the battery 20. Some notable and exemplary external power sources include, but are not limited to, AC-DC converters and vehicle alternators connected to the AC grid via a wall-mounted power outlet.

[0056] In many battery configurations, each of the first current collector 32, negative electrode 22, separator 26, positive electrode 24, and second current collector 34 is fabricated as a relatively thin layer (e.g., from a few micrometers to a fraction of a millimeter or less) and assembled into layers connected in an electrically parallel arrangement to provide suitable energy and power encapsulation. In various aspects, battery 20 may also include a variety of other components, although not shown herein, which are known to those skilled in the art. For example, battery 20 may include a housing, gaskets, terminal caps, tabs, battery terminals, and any other conventional components or materials that may be located within battery 20, including between or around the negative electrode 22, positive electrode 24, and / or separator 26. Figure 1 The battery 20 shown includes a liquid electrolyte 30 and illustrates a representative concept of battery operation.

[0057] The size and shape of battery 20 can vary depending on the specific application it is designed for. For example, battery-powered vehicles and handheld consumer electronics are two examples of batteries 20 that are most likely to be designed with different sizes, capacities, and power output specifications. Battery 20 can also be connected in series or parallel with other similar lithium-ion batteries or battery packs to generate greater voltage output, energy, and power, if required by the load device 42. Thus, battery 20 can generate current to load device 42, which is part of external circuit 40. When battery 20 discharges, load device 42 can be powered by the current flowing through external circuit 40. While electrical load device 42 can be any number of known electrical devices, some specific examples include electric motors for electric vehicles, laptop computers, tablet computers, cellular phones, and cordless power tools or appliances. Load device 42 can also be a generator that charges battery 20 to store electrical energy.

[0058] Continue to refer to Figure 1The positive electrode 24, negative electrode 22, and separator 26 may each include an electrolyte solution or system 30 within their pores, capable of conducting lithium ions between the negative electrode 22 and the positive electrode 24. Any suitable electrolyte 30 capable of conducting lithium ions between the negative electrode 22 and the positive electrode 24, whether in solid, liquid, semi-solid, or gel form, can be used in the lithium-ion battery 20. For example, in some aspects, the electrolyte 30 may be a non-aqueous liquid electrolyte solution (e.g., >1M) comprising a lithium salt dissolved in an organic solvent or a mixture of organic solvents. Many conventional non-aqueous liquid electrolyte solutions 30 can be used in the battery 20.

[0059] A non-limiting list of lithium salts that can be dissolved in organic solvents to form non-aqueous liquid electrolyte solutions includes lithium hexafluorophosphate (LiPF6), lithium perchlorate (LiClO4), lithium tetrachloroaluminate (LiAlCl4), lithium iodide (LiI), lithium bromide (LiBr), lithium thiocyanate (LiSCN), lithium tetrafluoroborate (LiBF4), lithium tetraphenylborate (LiB(C6H5)4), lithium bis(oxalato)borate (LiB(C2O4)2)(LiBOB), lithium difluorooxalato)borate (LiBF2(C2O4)), lithium hexafluoroarsenate (LiAsF6), lithium trifluoromethanesulfonate (LiCF3SO3), lithium bis(trifluoromethane)sulfonylimide (LiN(CF3SO2)2), lithium bis(fluorosulfonyl)imide (LiN(FSO2)2)(LiSFI), and combinations thereof. These and other similar lithium salts can dissolve in a variety of non-aqueous, non-protic organic solvents, including but not limited to various alkyl carbonates, such as cyclic carbonates (e.g., ethylene carbonate (EC), propylene carbonate (PC), butyl carbonate (BC), fluoroethylene carbonate (FEC), ethylene carbonate (VC), etc.), linear carbonates (e.g., dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), etc.), aliphatic carboxylic acid esters (e.g., methyl formate, methyl acetate, methyl propionate, etc.), γ-lactones (e.g., γ-butyrolactone, γ-valerolactone, etc.), chain ethers (e.g., 1,2-dimethoxyethane, 1,2-diethoxyethane, ethoxymethoxyethane, etc.), cyclic ethers (e.g., tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane, etc.), sulfur compounds (e.g., sulfolane), and combinations thereof.

[0060] The separator 26 may be a porous separator. For example, in some cases, the separator 26 may be a microporous polymer separator, including, for example, a polyolefin. The polyolefin may be a homopolymer (derived from a single monomer component) or a heteropolymer (derived from more than one monomer component), and may be linear or branched. If the heteropolymer is derived from two monomer components, the polyolefin may exhibit any copolymer chain arrangement, including block copolymers or random copolymers. Similarly, if the polyolefin is a heteropolymer derived from more than two monomer components, it may also be a block copolymer or a random copolymer. In some aspects, the polyolefin may be polyethylene (PE), polypropylene (PP), or a mixture of polyethylene (PE) and polypropylene (PP), or a multilayer porous membrane of PE and / or PP. Commercially available polyolefin porous separators 26 include those available from Celgard LLC. 2500 (single-layer polypropylene partition) and 2320 (Three-layer polypropylene / polyethylene / polypropylene partition).

[0061] When the separator 26 is a microporous polymer separator, it can be a single-layer or multi-layer laminated material, manufactured by dry or wet processes. For example, in some cases, a single layer of polyolefin can form the entire separator 26. In other aspects, the separator 26 can be a fibrous member having a large number of pores extending between opposing surfaces and can have an average thickness of, for example, less than 1 mm. However, as another example, multiple discrete layers of similar or dissimilar polyolefins can be assembled to form the microporous polymer separator 26. In addition to polyolefins, the separator 26 may also include other polymers, such as, but not limited to, polyethylene terephthalate (PET), polyvinylidene fluoride (PVdF), polyamides, polyimides, poly(amide-imide) copolymers, polyetherimides, and / or cellulose, or any other material suitable for producing a porous structure. The polyolefin layer and any other optional polymer layer may be further included as fibrous layers in the separator 26 to help the separator 26 have suitable structural and porous characteristics.

[0062] In some aspects, the partition 26 may also include one or more of a ceramic material and a heat-resistant material. For example, the partition 26 may also be mixed with a ceramic material and / or a heat-resistant material. The ceramic material and / or the heat-resistant material may be disposed on one or more sides of the partition 26. The ceramic material may be selected from alumina (Al2O3), silicon dioxide (SiO2), and combinations thereof. The heat-resistant material may be selected from NOMEX. TM Meta-aromatic polyamides (e.g., aromatic polyamides formed by the condensation reaction of monomers m-phenylenediamine and isophthaloyl chloride), ARAMID aromatic polyamides, and combinations thereof.

[0063] Various conventionally available polymers and commercial products for forming the separator 26 were considered, as well as many manufacturing methods that can be used to produce such a microporous polymer separator 26. For example, in some variations, the partition 26 may be a polyolefin-based partition, including, for example, polyacetylene, propylene (PP), and / or polyethylene (PE); a cellulose partition, including, for example, polyvinylidene fluoride (PVDF) components and / or porous polyimide components; and / or a high-temperature stable partition, including, for example, polyimide (PI) nanofiber-based nonwoven components, nano-alumina (Al2O3) and poly(lithium 4-styrene sulfonate) coated polyethylene components, silica (SiO2) coated polyethylene (PE) components, copolyimide coated polyethylene components, polyetherimide (PEI) (bisphenol-acetone phthalic anhydride (BPADA) and p-phenylenediamine) components, expanded polytetrafluoroethylene reinforced polyvinylidene fluoride-hexafluoropropylene components, and / or sandwich structure polyvinylidene fluoride (PVDF)-poly(m-phenylene isophthalamide) (PMIA)-polyvinylidene fluoride (PVDF) components. In each case, the separator 26 may have an average thickness greater than or equal to about 1 micrometer (tm) to less than or equal to about 50 tm, and in some cases, optionally greater than or equal to about 1 tm to less than or equal to about 20 tm; and the electrolyte 30 may wet a total porosity of the separator 26 greater than or equal to about 5 vol% to less than or equal to about 100 vol%.

[0064] In all aspects, such as Figure 1 The porous separator 26 and / or the electrolyte 30 disposed within the porous separator 26 can be replaced by a solid electrolyte (“SSE”) and / or a semi-solid electrolyte (e.g., a gel) that serves as both an electrolyte and a separator. For example, the solid electrolyte and / or semi-solid electrolyte can be disposed between the positive electrode 24 and the negative electrode 22. The solid electrolyte and / or semi-solid electrolyte facilitates lithium-ion transfer while providing mechanical separation and electrical insulation between the negative electrode 22 and the positive electrode 24.

[0065] The solid electrolyte and / or semi-solid electrolyte may include a plurality of solid electrolyte particles. In certain variants, the electrolyte 30 may at least partially fill the voids (e.g., interparticle pores) between the solid electrolyte particles defining the separator 26. In each variant, the solid electrolyte particles may include, for example, oxide-based solid particles (e.g., garnet-type solid particles (e.g., Li7La3Zr2O12 (LLZO)), perovskite-type solid particles (e.g., Li3xLa2 / 3-xTiO3, where 0 < x < 0.167), NASICON-type solid particles (e.g., Li1.4Al0.4Ti1.6(PO4)3, Li1+xAlxGe2-x(PO4)3 (where 0 ≤ x ≤ 2) (LAGP)) and / or LISICON-type solid particles (e.g., Li2+2xZn1-xGeO4, where 0 < x < 1)), metal-doped or aliovalent-substituted oxide solid particles (e.g., aluminum (Al) or niobium (Nb)-doped Li7La3Zr2O12, antimony (Sb)-doped Li7La3Zr2O12, gallium (Ga)-substituted Li7La3Zr2O12, chromium (Cr) and / or vanadium (V)-substituted LiSn2P3O12 and / or aluminum (Al)-substituted Li1+x+yAlxTi2-xSiYP3-yO12 (where 0 < x < 2 and 0 < y < 3)), sulfide-based solid particles (e.g., Li2S–P2S5 systems (e.g., Li3PS4, Li7P3S11 and Li9.6P3S12), Li2S–SNS2 systems (e.g., Li4SnS4), Li10GeP2S12 (LGPS), Li3.25Ge0.25P0.75S4 (thio-LISICON), Li3.4Si0.4P0.6S4, Li10GeP2S11.7O0.3, lithium silver thiophosphate (Li6PS5X, where X is Cl, Br or I), Li9.54Si1.74P1.44S11.7Cl0.3, Li9.6P3S12, Li7P3S11, Li9P3S9O3, Li10.35Ge1.3P1.65S12, Li10.35Si1.35P1.65S12, Li9.81Sn0.81P2.18S12, Li10(Si0.5Ge0.5)P2S12, Li10(Ge0.5Sn0.5)P2S12, Li10(Si0.5Sn0.5)P2S12, Li3.933Sn0.833As0.166S4, Li1-Li4SnS4 and / or Li4SnS4), nitride-based solid particles (e.g., Li3N, Li7PN4 and / or LiSi2N3), hydride-based solid particles (e.g., LiBH4, LiBH4–LiX (where X = Cl, Br or I), LiNH2, Li2NH, LiBH4–LiNH2 and / or Li3AlH6), halide-based solid particles (e.g., Li3YCl6, Li3InCl6, Li3YBr6, LiI, Li2CdCl4, Li2MgCl4, LiCdI4, Li2ZnI4 and / or Li3OCl), and / or borate-based solid particles (Li2B4O7 and / or Li2O-B2O3-P2O5).

[0066] The semi-solid electrolyte may include a polymer matrix and a liquid electrolyte. The polymer matrix may include, for example, polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP), polyethylene oxide (PEO), polypropylene oxide (PPO), polyacrylonitrile (PAN), polymethyl methacrylate (PMAN), polymethyl methacrylate (PMMA), carboxymethyl cellulose (CMC), polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP), and combinations thereof. The liquid electrolyte may be similar to electrolyte 30 as detailed above. In some variations, a semi-solid or gel electrolyte may also be present in the negative electrode 22 and / or the positive electrode 24.

[0067] Refer again Figure 1 The positive electrode 24 is formed of a lithium-based active material capable of lithium intercalation and deintercalation, alloying and dealloying, or electroplating and stripping, and serves as the positive terminal of a lithium-ion battery. The positive electrode 24 may be defined by a plurality of electroactive material particles. These electroactive material particles may be disposed in one or more layers to define the three-dimensional structure of the positive electrode 24. An electrolyte 30 may be introduced, for example, after battery assembly and contained within the pores of the positive electrode 24 (i.e., within the voids or spaces between the electroactive material particles). In some variations, the positive electrode 24 may comprise a plurality of solid electrolyte particles dispersed with the electroactive material particles. The electrolyte 30 may at least partially fill the voids or spaces between the electroactive material particles and the solid electrolyte particles. In each case, the positive electrode 24 may have an average thickness greater than or equal to about 30 μm and less than or equal to about 500 μm, and in some aspects, optionally greater than or equal to about 50 μm and less than or equal to about 100 μm.

[0068] In various aspects, the positively active materials include layered oxides represented by LiMeO2, where Me is a transition metal, such as cobalt (Co), nickel (Ni), manganese (Mn), iron (Fe), aluminum (Al), vanadium (V), or combinations thereof. In other variations, the positively active materials include polyanionic oxides represented by LiMePO4, where Me is a transition metal, such as cobalt (Co), nickel (Ni), manganese (Mn), iron (Fe), aluminum (Al), vanadium (V), or combinations thereof. In other variations, the positively active materials include monoclinic oxides represented by Li3Me2(PO4)3, where Me is a transition metal, such as cobalt (Co), nickel (Ni), manganese (Mn), iron (Fe), aluminum (Al), vanadium (V), or combinations thereof. In other variations, the positively active materials include spinel-type oxides represented by LiMe2O4, where Me is a transition metal, such as cobalt (Co), nickel (Ni), manganese (Mn), iron (Fe), aluminum (Al), vanadium (V), or combinations thereof. In other variations, the positively active material includes titanate vanadium ore represented by LiMeSO4F and / or LiMePO4F, where Me is a transition metal such as cobalt (Co), nickel (Ni), manganese (Mn), iron (Fe), aluminum (Al), vanadium (V), or a combination thereof.

[0069] In another variation, the positive electrode 24 may be a composite electrode comprising a combination of positively active materials. For example, the positive electrode 24 may comprise a first positively active material and a second positively active material. The mass ratio of the first positively active material to the second positively active material may be greater than or equal to about 5:95 to less than or equal to about 95:5. In some variations, the first and second positively active materials may be independently selected from one or more layered oxides, one or more olivine-type oxides, one or more monoclinic oxides, one or more spinel-type oxides, one or more titanate, or combinations thereof.

[0070] In each variant, the positively active material may be lithiated before or after being incorporated into the positive electrode 24 and / or the battery 20 to help compensate for lithium loss during cycling, such as lithium loss that may occur during the conversion reaction and / or the cathode-electrolyte interface (CEI) layer on the positive electrode 24 during the first cycle, and ongoing lithium loss due to, for example, the formation of a continuous cathode-electrolyte interface (CEI) layer.

[0071] In each variant, the positively active material may optionally be mixed with an electronically conductive material (i.e., a conductive additive) that provides an electronic conduction path and / or a polymeric binder material that improves the structural integrity of the positive electrode 24. For example, the positive electrode 24 may comprise more than or equal to about 70% by weight and less than or equal to about 98% by weight, and in some aspects, optionally more than or equal to about 80% by weight and less than or equal to about 97% by weight of the positively active material; more than or equal to 0% by weight and less than or equal to about 30% by weight, and optionally more than 0% by weight and less than or equal to about 30% by weight, and in some aspects, optionally more than or equal to about 0.5% by weight and less than or equal to about 10% by weight of the conductive material; and more than or equal to 0% by weight and less than or equal to about 20% by weight, and optionally more than 0% by weight and less than or equal to about 20% by weight, and in some aspects, optionally more than or equal to about 0.5% by weight and less than or equal to about 10% by weight of the polymeric binder.

[0072] Example polymer adhesives include polyimide, polyamic acid, polyamide, polysulfone, polyvinylidene fluoride (PVdF), polyvinylidene fluoride-hexafluoropropylene copolymer (PVdF-HFP), polytetrafluoroethylene (PTFE), polyacrylic acid (PAA), polychlorotrifluoroethylene, ethylene propylene diene monomer (EPDM), carboxymethyl cellulose (CMC), nitrile rubber (NBR), styrene-butadiene rubber (SBR), lithium polyacrylate (LiPAA), sodium polyacrylate (NaPAA), sodium alginate, lithium alginate, and / or styrene copolymer (SEBS). Electronically conductive materials may include, for example, carbon-based materials, powdered nickel or other metal particles, or conductive polymers. Carbon-based materials may include, for example, graphite, acetylene black (e.g., KETCHEN). TM Black or Denka TM Particles of conductive carbon black, carbon nanofibers and nanotubes (e.g., single-walled carbon nanotubes (SWCNTs), multi-walled carbon nanotubes (MWCNTs)), graphene (e.g., graphene sheets (GNPs), graphene oxide sheets), conductive carbon black (e.g., SuperP (SP)), etc. Examples of conductive polymers include polyaniline, polythiophene, polyacetylene, polypyrrole, etc.

[0073] The negative electrode 22 is formed of a lithium host material that can serve as the negative terminal of a lithium-ion battery. In various aspects, the negative electrode 22 can be defined by a plurality of negative electroactive material particles. The negative electroactive material particles can be disposed in one or more layers to define the three-dimensional structure of the negative electrode 22. The electrolyte 30 can be introduced, for example, after battery assembly and be contained within the pores of the negative electrode 22 (i.e., within the voids or spaces between the negative electroactive material particles). In certain variations, the negative electrode 22 can include a plurality of solid electrolyte particles dispersed with negative electroactive material particles. The electrolyte 30 can at least partially fill the voids or spaces between the negative electroactive material particles and the solid electrolyte particles. In each case, the negative electrode 22 can have an average thickness greater than or equal to about 30 μm and less than or equal to about 500 μm, and in certain aspects, optionally greater than or equal to about 50 μm and less than or equal to about 100 μm.

[0074] In certain variations, the negative electroactive material particles can include a silicon-containing (or silicon-based) electroactive material. The silicon-containing electroactive material can include silicon, lithium-silicon alloys, and other silicon-containing binary and / or ternary alloys. For example, in certain variations, the silicon-containing electroactive material can include elemental silicon (Si), various lithium silicide phases (LixSiy, where 0 < x < 17 and 1 < y < 4), silicon nanoparticles embedded in a silicon oxide (SiOx, where 0 < x < 2) matrix, lithium-doped silicon oxide (LiySiOx, where 0 < x < 2 and 0 < y < 1), and combinations thereof. The silicon-containing electroactive material can be provided in the form of nanoparticles, nanofibers, nanotubes, and / or micron particles.

[0075] In other variations, the negative electrode 22 can include one or more other alloy anode materials, such as aluminum, germanium, tin, antimony, and / or bismuth. In other variations, the negative electrode 22 can include a lithium-containing negative electroactive material, such as a lithium alloy and / or lithium metal. For example, in certain variations, the negative electrode 22 can be defined by a lithium metal foil. In other variations, the negative electrode 22 can include, by way of example only, a carbonaceous negative electroactive material (such as graphite, hard carbon, soft carbon, etc.) and / or a metal active material (such as tin, aluminum, magnesium, germanium, and their alloys, etc.).

[0076] In other variations, the negative electrode 22 may be a composite electrode comprising a combination of negatively active materials. For example, the negative electrode 22 may comprise a first negatively active material and a second negatively active material. The ratio of the first negatively active material to the second negatively active material may be greater than or equal to about 5:95 to less than or equal to about 95:5. In some variations, the first negatively active material may be an alloy anode material, including, for example, silicon, aluminum, germanium, and / or tin; the second negatively active material may comprise a carbon-containing material (e.g., graphite, hard carbon, and / or soft carbon). For example, in some variations, the negatively active material may comprise a carbonaceous-silicon-based composite material, comprising, for example, about 10% by weight of SiOx (where 0 ≤ x ≤ 2) and about 90% by weight of graphite.

[0077] In each variant, the negatively active material may be lithiated before or after incorporation into the negative electrode 22 and / or battery 20 to help compensate for lithium losses during cycling, such as lithium losses that may occur during the conversion reaction on the negative electrode 22 and / or the formation of the LixSi and / or solid electrolyte interface (SEI) layer (not shown) during the first cycle, as well as ongoing lithium losses due to, for example, the formation of a continuous solid electrolyte interface (SEI).

[0078] The negatively active material may also be optionally mixed with an electronically conductive material (i.e., a conductive additive) that provides an electron conduction path and / or a polymeric binder material that improves the structural integrity of the negative electrode 22. For example, the negative electrode 22 may comprise more than or equal to about 30% by weight and less than or equal to about 98% by weight, and in some aspects, optionally more than or equal to about 60% by weight and less than or equal to about 95% by weight of the negatively active material; more than or equal to 0% by weight and less than or equal to about 30% by weight, optionally more than 0% by weight and less than or equal to about 30% by weight, and in some aspects, optionally more than or equal to about 0.5% by weight and less than or equal to about 10% by weight of the electronically conductive material; and more than or equal to 0% by weight and less than or equal to about 20% by weight, optionally more than 0% by weight and less than or equal to about 20% by weight, and in some aspects, optionally more than or equal to about 0.5% by weight and less than or equal to about 10% by weight of the polymeric binder. The conductive additives and / or binders contained in the negative electrode 22 may be the same as or different from those contained in the positive electrode 24.

[0079] In various respects, this disclosure provides apparatus and methods for pre-forming a cathode electrolyte interface on a positive electrode material for use in an electrochemical cell, the electrochemical cell being similar to... Figure 1 The battery 20 shown. For example, Figure 2An example electrochemical reactor (e.g., an electrochemical stirred tank) 200 is shown, which can be a batch or continuous reactor for non-in-situ electrochemical pre-formation of a cathode-electrolyte interface (CEI) on a positively active material. The tank 200 is configured to contain or carry an electrolyte 230, which can be a continuously or intermittently replenished or replaced liquid. For example, in some variations, the tank 200 may also include a stirrer 250 configured to cause movement of the electrolyte 230. The electrolyte 230 may comprise a lithium salt and an organic solvent or a mixture of organic solvents, as described above. Figure 1 Electrolyte 30 is detailed in the context of the above.

[0080] The can 200 may be a conductive container, including one or more conductive components, such as conductive current collectors 232 and 234, disposed near or along one or more sides. For example, as shown, the can 200 may include a first current collector 232 disposed along a first side 202 of the can 200 and a second current collector 234 disposed along a second side 204 of the can 200. The first current collector 232 and the second current collector 234 are each in contact with the electrolyte 230. The one or more current collectors 232 and 234 may be high surface area current collectors made of copper, platinum, silver, etc. For example, the one or more current collectors 232 and 234 may have a surface area greater than or equal to about 1 cm². 2 / (cm 2 (Geometric) to less than or equal to approximately 10 cm 2 / (cm 2 The surface area (i.e., roughness factor) of the geometry.

[0081] Tank 200 may also include an additional cation source, such as lithium source 222, wherein the cation is lithium. Lithium source 222 is at least partially disposed within electrolyte 230 in tank 200 and is electrically connected to one of one or more current collectors 232, 234. In some variations, as shown, lithium source 222 may be electrically connected to a second current collector 234. For example, an interruptible external circuit 240 and a load device or voltage source 242 may be connected to lithium source 222 and second current collector 234. Lithium source 222 may have various configurations, including, for example, metal foil, foam and / or rods, and alternatively, cathode materials and / or lithium graphite. For example, in some variations, lithium source 222 may be a solid material, such as a lithium metal strip.

[0082] Although not shown, it should be understood that the electrochemical stirred tank 200 may include a variety of other components known to those skilled in the art, including, for example, a motor, inlet, outlet, port, associated piping, pressure, temperature and voltmeter / ammeter monitors and control systems connected to the stirrer.

[0083] Figure 3A The use of an electrochemical stirred tank, such as Figure 2The illustrated electrochemical stirred tank 200 represents an example method for pre-forming a cathode-electrolyte interface on an electroactive material. Method 300 may include contact 310 with the electroactive material or cathode active material (CAM) (e.g., electroactive cathode powder) 312 and an electrolyte 230. For example, in some variations, method 300 may include dispersion (e.g., suspension) in the electrolyte. The cathode active material includes multiple electroactive cathode material particles (e.g., lithium cobalt oxide (LCO), lithium nickel manganese cobalt oxide (NMC), lithium nickel manganese cobalt aluminum oxide (NMCA), lithium nickel manganese oxide (LNMO), lithium iron phosphate (LFO), lithium-rich manganese oxide (LMR), or lithium titanium oxide (LTO)).

[0084] In some variations, the cathode active material may be added to the electrochemical stirred tank 200 containing the electrolyte 230. In other variations, the cathode active material may be added to the electrolyte 230 before or during its addition to the electrochemical stirred tank 200. In each case, the resulting suspension may contain greater than or equal to about 1 gram (g) of cathode active material per 20 milliliters (mL) of electrolyte 230, and the electrolyte 230 may have a temperature greater than or equal to about 25°C and less than or equal to about 150°C, and in some aspects, optionally greater than or equal to about 40°C and less than or equal to about 150°C, such that the pre-formation of the cathode-electrolyte interface method can be considered a low-temperature process.

[0085] Current can be driven (or voltage can be supplied) to the electrochemical reactor 200, and depending on the operating time, the thickness of the CEI can be formed on the electroactive cathode material particles. One or more additives can be added to the electrolyte to alter the chemical properties of the electrolyte before or during the current being driven (or voltage being supplied) to the electrochemical reactor 200.

[0086] In some variations, method 300 includes providing or applying a current or voltage of 320 between a lithium source 222 and a second current collector 234 to pre-form a cathode electrolyte interface on the electroactive cathode material particles.

[0087] Reference Figure 3A At 310, the cathode active material is suspended in the electrolyte 230. A stirrer 250 can be used to stir the cathode active material in the electrolyte.

[0088] At 315, one or more of the additives introduced above can be added to the electrochemical reactor 200.

[0089] At 320, current can be driven (or voltage can be supplied) to the electrochemical reactor 200. (Reference) Figure 4A and 4B A voltage can be supplied to the electrochemical reactor 200 to initiate the decomposition of the electrolyte and / or additives. (Refer to...) Figure 5Aand 5B According to another aspect of the invention, current can be driven between the electrochemical reactor 200 and the lithium source 222 and the second conductive current collector 234 to delithiate and relithiate the cathode active material (i.e., cycle). According to one aspect, the current provided within the electrochemical reactor is greater than or equal to about 0.1 mA / cm². 2 to less than or equal to approximately 25 mA / cm 2 Current or voltage can be used to ionize and form cations at the cation source, which react with the cathode active material to pre-form a cathode electrolyte interface layer 322 on the cathode active material.

[0090] At 340, the cathode active material having the cathode electrolyte interface layer 322 can be filtered out from the electrolyte 230 and rinsed. According to one aspect, the electrolyte can be used to rinse the electroactive cathode material 312 having the cathode electrolyte interface layer 322. According to another aspect, the electrolyte can be reused for further processing in the electrochemical reactor 200. The electrolyte may include solvents such as dimethyl carbonate (DMC), ethylene carbonate (EC), diethyl carbonate (DEC), propylene carbonate (PC), methyl ethyl carbonate (EMC), dimethyl sulfoxide (DMSO), ethyl acetate (EA), γ-butyrolactone (GBL), 1,2-dimethoxyethane (DME), tetraethylene glycol dimethyl ether (TEGDME), or diethyl carbonate tetramethylene sulfone. Alternatively, the electrolyte may include a salt, such as lithium hexafluorophosphate (LiPF6), lithium bis(fluorosulfonyl)imide (LiFSI), lithium bis(fluorosulfonyl)imide (LiTFSI), lithium tetrafluoroborate (LiBF4), lithium perchlorate (LiClO4), lithium bis(oxalate)borate (LiBOB), or LiODF.

[0091] At 350, an electrode can be fabricated using electroactive cathode material particles 312 having a cathode electrolyte interface layer 322.

[0092] At 360, batteries including one or more electrodes can be assembled.

[0093] refer to Figure 3B Method 300' is provided. In general, method 300' is similar to method 300. However, in method 300', after 310 and before any additives are introduced into the electrochemical reactor, current is driven (or voltage is supplied) to the electrochemical reactor 200 at 320 to initiate electrolyte decomposition.

[0094] At 325, one or more additives are introduced into the electrochemical reactor 200, such as fluoroethylene carbonate (FEC), vinylene carbonate (VC), tetraethoxysilane (TEOS), (2-cyanoethyl)triethoxysilane (TEOSCN), dimethylacrylamide (DMAA), and / or methyl (2,2,2-trifluoroethyl) carbonate (FEMC).

[0095] At 330, current is driven (or voltage is supplied) to electrochemical reactor 200 to initiate further decomposition of the electrolyte and one or more additives added to the electrochemical reactor. According to one aspect, the current supplied within the electrochemical reactor is greater than or equal to about 0.1 mA / cm². 2 to less than or equal to approximately 25 mA / cm 2 .

[0096] Method 300' may follow one or more of the remaining steps of method 300.

[0097] refer to Figure 3C Method 300” is provided for pre-forming two or more layers of cathode electrolyte interface on electroactive cathode material particles. Generally, method 300” is similar to methods 300 and 300'. However, in order to form more than one layer of CEI on the electroactive cathode material particles, additives are added to the electrochemical reactor at 315 and 325, followed by current driving (or voltage supply) to the electrochemical reactor more than once (e.g., at 320 and 330). In other words, multiple addition steps can be introduced sequentially. According to one aspect, the electroactive cathode material particles can be rinsed before adding more additives and before current driving (or voltage supply) to the electrochemical reactor.

[0098] Methods 300, 300', 300" may include one or more constant current or constant potential steps.

[0099] Many embodiments have been described. However, it should be understood that various modifications can be made without departing from the spirit and scope of this disclosure. Therefore, other embodiments are also within the scope of the following claims.

[0100] The foregoing description has been provided for purposes of illustration and description. It is not intended to be exhaustive or limiting of this disclosure. Individual elements or features of a particular configuration are generally not limited to that particular configuration, but where applicable, they are interchangeable and can be used in selected configurations, even if not specifically shown or described. This can also be varied in many ways. Such variations should not be considered as departing from this disclosure, and all such modifications are intended to be included within the scope of this disclosure.

Claims

1. A method for pre-forming a cathode electrolyte interface on an electroactive material, the method comprising: An electric current or voltage is supplied to an electrochemical reactor comprising a cation source, an electrolyte mixture, one or more additives, and a cathode active material in contact with each other, wherein the electric current or voltage is used to ionize and form cations at the cation source, the cations reacting with the cathode active material to pre-form a cathode electrolyte interface on the cathode active material.

2. The method according to claim 1, wherein, The electrolyte mixture contains the cathode active material, and the method further includes: Before being placed in the electrochemical reactor, an electrolyte mixture is prepared by contacting the cathode active material with an electrolyte, wherein the electrolyte mixture contains greater than or equal to about 1 gram of cathode active material per 20 milliliters of electrolyte.

3. The method according to claim 2, wherein, The cathode active material is a positive electrode material.

4. The method according to claim 3, wherein, The cathode active material includes materials selected from the following: lithium nickel manganese cobalt oxide, lithium-rich manganese base oxide or lithium manganese oxide and any combination thereof.

5. The method according to claim 2, wherein, The cation source includes cations selected from the following: lithium, calcium, sodium, potassium, and any combination thereof.

6. The method according to claim 2, wherein, The one or more additives include materials selected from: lithium salt molecules, fluorinated organic molecules, or organometallic molecules.

7. The method according to claim 1, wherein, The current or voltage is provided for a period of time greater than or equal to about 5 hours and less than or equal to about 100 hours.

8. The method according to claim 1, wherein, The current or voltage is a first current or voltage, which is provided in a first time period, and the method further includes providing a second current or voltage in a second time period, wherein the second current or voltage is different from the first current or voltage.

9. The method according to claim 1, wherein, The method further includes one or more filtration steps, one or more rinsing steps, or a combination of one or more filtration steps and one or more rinsing steps to collect the electroactive material from the electrolyte mixture.

10. The method according to claim 1, wherein, The method further includes one or more constant current or constant potential steps.

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