METHOD FOR LITHIATION OF ELECTROACTIVE MATERIALS

Abstract

A process for producing a lithiated electroactive material, the process comprising: Dispersing a precursor for electroactive material (220, 320) in an electrolyte (210, 310) containing a lithium-based salt at room temperature to form an electrolyte mixture; Contacting the electrolyte mixture and a lithium source (240, 340) to cause the lithium source (240, 340) to ionize and release lithium ions (Li + to form lithium ions (Li + ) react with the precursor of the electroactive material (220, 320) in the electrolyte mixture to form the lithiated electroactive material; and where, after the reaction of the lithium ions (Li +) with the precursor for electroactive material (220, 320) in the electrolyte mixture the lithiated electroactive material is in a first state (222, 322), and the process further comprises the electrochemical discharge of the lithiated electroactive material to have less than or equal to 40% of the total lithium present in the lithiated electroactive material in the first state (222, 322); wherein the process for forming the lithiated electroactive material is a continuous process and the dispersion and contacting take place in a first container (230) and the electrochemical discharge in a second container (250), wherein the first and the second containers (230, 250) are formed of materials that are not reactive with the electrolyte mixture, and the first and second containers (230, 250) are in fluid communication and the lithiated electroactive material flows from the first container (230) to the second container (250); or wherein the lithium source (340) coats an inner channel (330) of a channel flow reactor and the electrolyte mixture migrates through the channel flow reactor; or wherein the lithium source (340) defines an internal surface of a channel flow reactor and the electrolyte mixture migrates through the channel flow reactor.

Description

INTRODUCTION

[0001] This section contains background information related to the present disclosure that does not necessarily represent the prior art.

[0002] The present disclosure relates to electroactive materials for use in electrodes of electrochemical lithium-ion cells and methods for their production, e.g. methods for the lithiation of electroactive materials.

[0003] Advanced energy storage and systems are in demand to meet the energy and / or power requirements of a wide variety of products, including automotive products such as start-stop systems (e.g., 12V start-stop systems), battery-powered systems, hybrid electric vehicles (HEVs), and electric vehicles (EVs). Typical lithium-ion batteries contain at least two electrodes and an electrolyte and / or separator. One of the two electrodes serves as the positive electrode or cathode, and the other serves as the negative electrode or anode. A separator and / or electrolyte may be positioned between the negative and positive electrodes. The electrolyte is suitable for conducting lithium ions between the electrodes and, like the two electrodes, can be in solid and / or liquid form and / or a hybrid thereof.In cases of solid-state batteries containing solid electrodes and a solid electrolyte, the solid electrolyte can physically separate the electrodes, so a separate separator is not required.

[0004] Conventional rechargeable lithium-ion batteries function by reversibly transferring lithium ions back and forth between the negative and positive electrodes. For example, during charging, lithium ions move from the positive electrode to the negative electrode, and during discharging, they move in the opposite direction. Such lithium-ion batteries can reversibly power an associated load device when needed. More precisely, a load device can be supplied with electrical energy by the lithium-ion battery until the lithium content of the negative electrode is effectively depleted. The battery can then be recharged by passing a suitable direct current in the opposite direction between the electrodes.

[0005] During discharge, the negative electrode can contain a relatively high concentration of lithium (e.g., trapped lithium), which is oxidized to lithium ions and electrons. Lithium ions can migrate from the negative electrode to the positive electrode, for example, through the ionically conductive electrolyte solution contained in the pores of an intervening porous separator. Simultaneously, the electrons traverse an external circuit from the negative electrode to the positive electrode. These lithium ions can be incorporated into the material of the positive electrode through an electrochemical reduction reaction. After a partial or complete discharge of its available capacity, the battery can be recharged or regenerated by an external power source, thereby reversing the electrochemical reactions that occurred during discharge.

[0006] Silicon has the highest known theoretical charge capacity, making it one of the most promising negative electroactive materials for rechargeable lithium-ion batteries. However, silicon also undergoes excessive volumetric expansion and contraction (e.g., 300%) during successive charging and discharging cycles. Furthermore, some of the stored lithium remains at the negative electrode after the first cycle, for example, due to the formation of a lithium oxide. xSilicon and / or a solid electrolyte interface (SEI) layer on the negative electrode during the first cycle, as well as ongoing lithium loss due to rupture of the continuous solid electrolyte interface, can lead to reduced specific energy and power in the battery due to additional positive electrode mass that does not contribute to the battery's reversible operation. For example, after the first cycle, the lithium-ion battery may exhibit an irreversible capacity loss of more than or equal to approximately 5% to less than or equal to approximately 30%. Lithiation, such as pre-lithiation, can compensate for such losses. However, conventional lithiation processes require the fabrication and degradation of half-cells and / or high-temperature chemical processes, which are time-consuming and often expensive.Accordingly, it would be desirable to develop improved electroactive and electrode materials and methods for their production for an electrochemical cell that can meet these challenges.

[0007] DE 10 2015 119 214 A1 discloses a process for forming porous materials. US 2011 / 0 244 328 A1 discloses a secondary battery with a non-aqueous electrolyte. US 2016 / 0 260 967 A1 discloses a process for producing a silicon:silicon oxide:lithium composite material (SSLC) that can be used as the active material for a negative electrode in non-aqueous battery cells. SUMMARY

[0008] The present invention relates to a method for producing a lithiated electroactive material according to claim 1.

[0009] This section contains a general summary of the revelation and is not a comprehensive revelation of its full scope or all of its features.

[0010] In various aspects, the present disclosure provides a method for forming a lithiated electroactive material at room temperature. The method includes, for example, dispersing an electroactive material precursor in a room-temperature electrolyte containing a lithium-based salt to form an electrolyte mixture; and contacting the electrolyte mixture with a lithium source to cause the lithium source to ionize and release lithium ions (Li). + to form lithium ions (Li). + The lithium ions (Li) can react with the precursor of the electroactive material in the electrolyte mixture to form the lithiated electroactive material. After the reaction of the lithium ions (Li), the lithiated electroactive material is located in the electrolyte mixture.+ The process involves the electrochemical discharge of the lithiated electroactive material to a second state, comprising the precursor of the electroactive material in the electrolyte mixture in a first state. The second state contains less than or equal to approximately 40% of the total lithium present in the lithiated electroactive material in the first state.

[0011] The process for forming the lithiated electroactive material is either a continuous process, in which dispersion and contacting take place in a first container and electrochemical discharge in a second container. Both the first and second containers consist of materials that are non-reactive with the electrolyte mixture. The first and second containers are in fluid communication, and the lithiated electroactive material flows from the first container to the second.

[0012] Or the lithium source coats an inner channel of a channel-flow reactor, and the electrolyte mixture migrates through the channel-flow reactor. Or the lithium source defines an inner surface of a channel-flow reactor, and the electrolyte mixture migrates through the channel-flow reactor.

[0013] In one aspect, the lithiated electroactive material is located after the reaction of the lithium ions (Li + ) with the precursor of the electroactive material in the electrolyte mixture in a first state, which is described by the formula Li 4,4x Si is denoted, where 0.75 ≤ x ≤ 1, and the process can further include the electrochemical discharge of the lithiated electroactive material to a second state. The second state can be described by the formula Li 4,4x Si are denoted, where 0.015 ≤ x ≤ 0.5.

[0014] In one aspect, the precursor of the electroactive material can be a silicon powder precursor. In the first state, the lithiated electroactive material Li 4,4 Si contained. In the second state, the lithiated electroactive material Li 0,8 They contain.

[0015] In one aspect, the first and second containers may contain one or more of the components stainless steel, nickel and copper.

[0016] In one aspect, the second container can contain a counter electrode. The counter electrode can contain one or more of graphite, lithium phosphate (Li3PO4) (LPO), and lithium titanate (Li2TiO3) (LTO).

[0017] In one aspect, the counter electrode can be located inside a separator.

[0018] In one aspect, the process can involve applying a bias voltage to the counter electrode. When the bias voltage is applied, the discharged lithium ions (Li) can be transferred to the electrode. +The particles from the lithiated electroactive particles migrate to the counter electrode to form the lithiated electroactive material with the second state. The bias voltage can be greater than or equal to approximately 0.1 V to less than or equal to approximately 24 V. The bias voltage can be applied for a period of time from more than or equal to approximately 1 minute to less than or equal to approximately 24 hours.

[0019] In one aspect, the counter electrode can contain one or more materials: graphite, lithium phosphate (Li3PO4) (LPO), and lithium titanate (Li2TiO3) (LTO). The container can contain one or more materials: stainless steel, nickel, and copper.

[0020] In one aspect, the discharged lithium ions (Li + ) are collected and recycled after the electrochemical discharge.

[0021] In one aspect, the process can still include isolating the lithiated electroactive material.

[0022] In various other aspects, the present disclosure provides a further method for the formation of a lithiated electroactive material at room temperature. The method may include dispersing a silicon powder precursor in an electrolyte at room temperature containing a lithium-based salt and contacting the electrolyte mixture with a lithium source to cause the lithium source to ionize and release lithium ions (Li). + to form lithium ions (Li). + ) can be combined with the silicon powder precursor to form Li 4,4x Si react, where 0.75 ≤ x ≤ 1. The method can further involve applying a bias voltage to a counter electrode in electrical connection with the Li 4,4x Si include to enable an electrochemical discharge of lithium ions (Li) + ) to effect, which differ from Li 4,4x Move Si to the counter electrode to Li 4,4x Si to form where 0.015 ≤ x ≤ 0.5.

[0023] In one aspect, the bias voltage can be greater than or equal to approximately 0.1 V to less than or equal to approximately 24 V. The bias voltage can be applied for a period of more than or equal to approximately 1 minute to less than or equal to approximately 24 hours.

[0024] Further areas of application will become apparent from the description given here. The description and specific examples in this summary serve only for illustration and are not intended to limit the scope of the present disclosure. DRAWINGS

[0025] The drawings described here serve only to illustrate selected embodiments and not all possible implementations, and are not intended to limit the scope of the present disclosure. Fig. Figure 1 is a schematic representation of an exemplary electrochemical battery that circulates or cyclically moves lithium ions; Fig. Figure 2 is a schematic representation of an exemplary continuous process for the lithiation of electroactive materials; and Fig. Figure 3 is a schematic representation of an exemplary channel flow process for the lithiation of electroactive materials.

[0026] The corresponding reference symbols designate corresponding parts in the different views of the drawings. DETAILED DESCRIPTION

[0027] The terminology used here serves only to describe certain exemplary embodiments and is not intended to be restrictive. As used here, the singular forms "a," "an," and "the" can also include the plural forms unless the context clearly indicates otherwise. The terms "comprises," "comprehensive," "containing," and "exhibiting" are inclusive and therefore specify the presence of indicated features, elements, compositions, steps, integers, processes, and / or components, but do not exclude the presence or addition of one or more other features, integers, steps, processes, elements, components, and / or groups thereof.Although the open term "comprehensive" is to be understood as a non-restrictive term used to describe and claim the various embodiments set forth herein, the term can alternatively be understood, under certain aspects, as a more restrictive term, such as "consisting of" or "consisting substantially of". Therefore, for each given embodiment that mentions compositions, materials, components, elements, features, integers, processes and / or process steps, the present disclosure expressly includes embodiments that consist of, or consist substantially of, such mentioned compositions, materials, components, elements, features, integers, processes and / or process steps.In the case of "consisting of", the alternative embodiment excludes all additional compositions, materials, components, elements, features, integers, operations and / or process steps, whereas in the case of "consisting substantially of", all additional compositions, materials, components, elements, features, integers, operations and / or process steps that substantially affect the basic and novel features are excluded from such an embodiment, but all compositions, materials, components, elements, features, integers, operations and / or process steps that do not substantially affect the basic and novel features may be included in the embodiment.

[0028] All procedural steps, processes, and procedures described here are not to be interpreted as necessarily having to be carried out in the discussed or depicted order, unless they are expressly designated as such. It is also understood that additional or alternative steps may be applied, unless otherwise specified.

[0029] When a component, element, or layer is described as "on," "interacting," "connected," or "coupled" with another element or layer, it may be directly on, interacting, connected, or coupled with that other component, element, or layer, or there may be intervening elements or layers. Conversely, when an element is described as "directly on," "directly interacting with," "directly connected with," or "directly coupled with" another element or layer, there must be no intervening elements or layers. Other words used to describe the relationship between elements should be interpreted similarly (e.g., "between" versus "directly between," "next to" versus "directly beside," etc.).As used here, the term “and / or” includes all combinations of one or more of the related listed elements.

[0030] Although the terms first, second, third, etc., may be used here to describe different steps, elements, components, areas, layers, and / or sections, these steps, elements, components, areas, layers, and / or sections should not be restricted by these terms unless otherwise specified. These terms should only be used to distinguish one step, element, component, area, layer, or section from another. Terms such as "first," "second," and other numerical terms, when used here, do not imply any sequence or order unless clearly indicated by the context.Thus, a first step, element, component, area, layer or section discussed below could be referred to as a second step, element, component, area, layer or section without deviating from the teachings of the exemplary embodiments.

[0031] Spatially or temporally relative terms such as "before," "after," "inside," "outside," "under," "below," "down," "above," "above," and the like may be used here for the sake of simplicity to describe the relationship of one element or feature to one or more other elements or features, as illustrated in the figures. Spatially or temporally relative terms may also be intended to encompass different orientations of the device or system in use or operation, in addition to the orientation shown in the figures.

[0032] Throughout this entire disclosure, numerical values ​​represent approximate measures or limits for ranges that include minor deviations from the stated values ​​and embodiments with approximately the stated value, as well as those with exactly the stated value. Unlike the working examples at the end of the detailed description, all numerical values ​​of parameters (e.g., of quantities or conditions) in this specification, including the appended claims, are to be understood as being modified in all cases by the term "approximately," regardless of whether "approximately" actually precedes the numerical value or not. "Approximately" means that the stated numerical value permits a slight inaccuracy (with some approximation to the accuracy of the value; approximately or quite close to the value; almost).Unless otherwise understood in engineering with this ordinary meaning, the imprecision indicated by "approximately" means, at a minimum, deviations that may arise from ordinary procedures for measuring and using such parameters. For example, "approximately" may include a variation of less than or equal to 5%, optionally less than or equal to 4%, optionally less than or equal to 3%, optionally less than or equal to 2%, optionally less than or equal to 1%, optionally less than or equal to 0.5%, and, in certain aspects, optionally less than or equal to 0.1%.

[0033] Furthermore, the disclosure of ranges includes the disclosure of all values ​​and further subdivided ranges within the entire range, including the endpoints and the subranges specified for the ranges.

[0034] Exemplary embodiments are now described in more detail with reference to the attached drawings.

[0035] The present invention relates to a method for producing a lithiated electroactive material according to claim 1.

[0036] The present technology relates to electroactive materials for use in electrodes of electrochemical lithium-ion cells and methods for their production, for example, methods for the lithiation of electroactive materials to reduce operational inefficiencies resulting, for instance, from the loss of active lithium ions during the first cell cycle. For example, the method generally involves dispersing a precursor for the electroactive material in an electrolyte containing a lithium base salt to form an electrolyte mixture; contacting the electrolyte mixture with a lithium source to ionize and form lithium ions, which react with the precursor of the electroactive material to form a lithiated electroactive material. The lithiated electroactive material may exhibit a partial or complete state of lithiation, e.g., more than 70% of the total lithiation.In certain cases, the process may involve the electrochemical discharge of the lithiated electroactive material to a second or optimized state of lithiation, e.g. with less than or equal to about 40% lithium, compared to lithiated electroactive materials in the first state.

[0037] A typical lithium-ion battery comprises a first electrode (e.g., a positive electrode or cathode) opposite a second electrode (e.g., a negative electrode or anode), and a separator and / or electrolyte between them. In a lithium-ion battery pack, batteries or cells can often be electrically connected in a stacked or coiled configuration to increase overall power. Lithium-ion batteries operate by reversibly transporting lithium ions between the first and second electrodes. For example, lithium ions can move from the positive electrode to the negative electrode during charging and in the opposite direction during discharging. The electrolyte is suitable for conducting lithium ions and can be in liquid, gel, or solid form.An exemplary and schematic representation of an electrochemical cell (also called a battery) 20 is shown in . Fig. 1 shown. Although the example shown includes a single cathode 24 and a single anode 22, it is clear to those skilled in the art that the teachings presented here extend to various other configurations, including those with one or more cathodes and one or more anodes, as well as various current collectors with electroactive layers arranged on or beside one or more surfaces thereof.

[0038] The battery 20 contains a negative electrode 22, a positive electrode 24, and a separator 26 located between the electrodes 22 and 24. The separator 26 provides electrical isolation—preventing physical contact—between the electrodes 22 and 24. Furthermore, the separator 26 offers a path of minimal resistance for the internal passage of lithium ions and, in certain cases, associated anions during the cyclic movement of the lithium ions. In some configurations, the separator 26 includes an electrolyte 30, which may also be present in the negative electrode 22 and the positive electrode 24. In certain variations, the separator 26 can be formed by a solid electrolyte 30. For example, the separator 26 can be defined by a variety of solid electrolyte particles (not shown).

[0039] A current collector 32 for the negative electrode can be positioned at or near the negative electrode 22, and a current collector 34 for the positive electrode can be positioned at or near the positive electrode 24. The current collector 32 for the negative electrode and the current collector 34 for the positive electrode each collect free electrons and move them to and from an external circuit 40. For example, an interruptible external circuit 40 and a load device 42 can connect the negative electrode 22 (via the current collector 32 of the negative electrode) and the positive electrode 24 (via the current collector 34 of the positive electrode). The current collector 34 of the positive electrode can be a metal foil, a metal grid or screen, or expanded metal made of aluminum or another suitable electrically conductive material known to those skilled in the art.The current collector 32 of the negative electrode can be a metal foil, a metal grid or screen, or expanded metal made of copper or another suitable electrically conductive material known to those skilled in the art.

[0040] The battery 20 can generate an electric current during discharge through reversible electrochemical reactions that occur when the external circuit 40 is closed (to connect the negative electrode 22 and the positive electrode 24) and the negative electrode 22 contains a relatively larger amount of lithium than the positive electrode 24. The chemical potential difference between the positive electrode 24 and the negative electrode 22 drives the electrons generated by the oxidation of the lithium stored at the negative electrode 22 through the external circuit 40 towards the positive electrode 24. Lithium ions, also generated at the negative electrode 22, are simultaneously transported to the positive electrode 24 through the electrolyte 30 contained in the separator 26.The electrons flow through the external circuit 40, and the lithium ions migrate through the separator 26, which contains the electrolyte solution 30, to form lithium deposited at the positive electrode 24. The electric current flowing through the external circuit 40 can be utilized and passed through the load device 42 until the available lithium in the negative electrode 22 is consumed and the capacity of the battery 20 has decreased.

[0041] The battery 20 can be charged or recharged at any time by connecting an external power source to it, thus reversing the electrochemical reactions that occur during battery discharge. Connecting an external electrical energy source to the battery 20 promotes a reaction, such as the non-spontaneous oxidation of stored lithium, at the positive electrode 24, generating electrons and lithium ions. The lithium ions flow through the electrolyte 30, via the separator 26, back to the negative electrode 22, replenishing it with lithium (e.g., stored lithium) for use during the next battery discharge cycle. Thus, a complete discharge followed by a complete charge is considered a cycle in which lithium ions are cyclically moved between the positive electrode 24 and the negative electrode 22.The external power source that can be used to charge battery 20 can vary depending on the size, design, and specific end application of battery 20. Some notable and exemplary external power sources include an AC-DC converter connected to an AC power supply via a wall socket, and a motor vehicle alternator.

[0042] In many configurations of the lithium-ion battery, the current collector 32 for the negative electrode, the negative electrode 22, the separator 26, the positive electrode 24, and the current collector 34 for the positive electrode are each manufactured as relatively thin layers (e.g., from a few micrometers to a fraction of a millimeter or less thick) and assembled in electrically parallel layers to obtain a suitable electrical energy and power package. In various aspects, the battery 20 may also contain a variety of other components, which, although not shown here, are nevertheless known to those skilled in the art. For example, the battery 20 may include an outer casing, seals, terminal caps, and any other conventional components or materials that may be found inside the battery 20, including, but not limited to,between or around the negative electrode 22, the positive electrode 24, and / or the separator 26. The battery 20 described above contains a liquid electrolyte and illustrates representative concepts of battery operation. However, the battery 20 can also be a solid-state battery containing a solid electrolyte, which may have a different structure, as is known to those skilled in the art.

[0043] As mentioned above, the size and shape of the battery 20 can vary depending on the specific applications for which it is designed. Battery-powered vehicles and portable consumer electronics devices are two examples where the battery 20 is most likely to be designed according to different size, capacity, and power specifications. The battery 20 can also be connected in series or parallel with other similar lithium-ion cells or batteries to produce a higher output voltage, energy, and power when required by the load device 42. Accordingly, the battery 20 can generate electrical current for a load device 42 that is part of the external circuit 40. The load device 42 can be powered wholly or partially by the electrical current flowing through the external circuit 40 as the lithium-ion battery 20 is discharged.

[0044] The electrical load device 42 can be any number of known electrically powered devices. Some specific examples are an electric motor for an electric vehicle, a laptop computer, a tablet computer, a mobile phone, and cordless power tools or devices. The load device 42 can also be a power-generating device that charges the battery 20 for the purpose of storing electrical energy.

[0045] With renewed reference to Fig. 1. The positive electrode 24, the negative electrode 22, and the separator 26 can each contain an electrolyte solution or electrolyte system 30, for example, within their pores, capable of conducting lithium ions between the negative electrode 22 and the positive electrode 24. Any suitable electrolyte 30, whether in solid, liquid, or gel form, that can conduct lithium ions between the electrodes 22 and 24 can be used in the battery 20. For example, the electrolyte 30 can be a non-aqueous liquid electrolyte solution containing a lithium salt dissolved in an organic solvent or a mixture of organic solvents. Numerous conventional non-aqueous liquid electrolyte solutions can be used in the battery 20.

[0046] Suitable lithium salts generally have inert anions. A non-restrictive list of lithium salts that may be dissolved in an organic solvent or a mixture of organic solvents to form the non-aqueous liquid electrolyte solution includes lithium hexafluorophosphate (LiPF6); Lithium perchlorate (LiClO4), lithium tetrachloroaluminate (LiAlCl4), lithium iodide (Lil), lithium bromide (LiBr), lithium thiocyanate (LiSCN), lithium tetrafluoroborate (LiBF4), lithium difluorooxalatoborate (LiBF2(C2O4)) (LiODFB), lithium tetraphenylborate (LiB(C6H5)4), lithium bis(oxalate)borate (LiB(C2O4)2) (LiBOB), lithium tetrafluorooxalatophosphate (LiPF4(C2O4)) (LiFOP), lithium nitrate (LiNO3), lithium hexafluoroarsenate (LiAsF6), lithium trifluoromethanesulfonate (LiCF3SO3), lithium bis(trifluoromethanesulfonimide) (LiTFSI) (LiN(CF3SO2)2), lithium fluorosulfonylimide (LiN(FSO2)2) (LiFSI), lithium fluoroalkylphosphate (LiFAP) (Li3O4P) and combinations thereof.

[0047] These and other similar lithium salts can be dissolved in a variety of organic solvents, including, but not limited to, various alkyl carbonates such as cyclic carbonates (e.g., ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), fluoroethylene carbonate (FEC)), linear carbonates (e.g., dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC)), aliphatic carboxylic esters (e.g., methyl formate, methyl acetate, methyl propionate), γ-lactones (e.g., γ-butyrolactone, γ-valerolactone), chain ethers (e.g., 1,2-dimethoxyethane (DME), 1,2-diethoxyethane, ethoxymethoxyethane), cyclic ethers (e.g., tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane (DOL)), sulfur compounds (e.g., sulfolane), and combinations thereof. In various aspects, the electrolyte can contain a concentration of more than or equal to 1 M to less than or equal to approximately 2 M of one or more lithium salts. In certain variations, e.g.For example, if the electrolyte has a lithium concentration of more than approximately 2 M or is an ionic liquid, the electrolyte may contain one or more diluents, such as fluoroethylene carbonate (FEC) and / or hydrofluoroether (HFE).

[0048] The solid electrolyte can contain one or more solid electrolyte particles, which may include one or more polymer-based particles, oxide-based particles, sulfide-based particles, halide-based particles, borate-based particles, nitride-based particles, and hydride-based particles. Such a solid electrolyte can be arranged in a variety of layers to define a three-dimensional structure and, in certain aspects, the separator 26. In various aspects, the polymer-based particles can be mixed with a lithium salt so that they act as a solid solvent.

[0049] In various aspects, the oxide-based particles can include one or more garnet ceramics, LISICON-type oxides, NASICON-type oxides, and perovskite-type ceramics. For example, one or more garnet ceramics can be selected from the group consisting of: Li 6‚5 La3Zr 1,75 Te 0,25 O 12 , Li7La3Zr2O 12 , Li 6,2 Ga 0,3 La 2,95 Rb 0,05 Zr2O 12 , Li 6,85 La 2,9 Approx 0,1 Zr 1,75 Note 0,25 O 12 , Li 6,25 Al 0,25 La3Zr2O 12 , Li 6,75 La3Zr 1,75 Note 0,25 O 12 , Li 6,75 La3Zr 1,75 Note 0,25 O 12 and combinations thereof. One or more LISICON-type oxides can be selected from the group consisting of: Li 14 Zn(GeO4)4, Li 3+x (P 1-x Si x )O4 (where 0 < x < 1), Li 3+x Ge x V 1-x O4 (where 0 < x < 1) and combinations thereof. The one or more oxides of the NASICON type can be defined by LiMM'(PO4)3, where M and M' are independently selected from Al, Ge, Ti, Sn, Hf, Zr, and La. For example, in certain variations, the one or more oxides of the NASICON type can be selected from the group consisting of: Li 1+x Al x Ge 2-x (PO4)3 (LAGP) (where 0 ≤ x ≤ 2), Li 1+x Al x Ti 2-x (PO4)3 (LATP) (where 0 ≤ x ≤ 2), Li 1+x Y x Zr 2-x (PO4)3 (LYZP) (where 0 ≤ x ≤ 2), Li 1,3 Al 0,3 Ti 1,7 (PO4)3, LiTi2(PO4)3, LiGeTi(PO4)3, LiGe2(PO4)3, LiHf2(PO4)3 and combinations thereof. One or more perovskite-type ceramics may be selected from the group consisting of: Li 3,3 La 0,53 TiO3, LiSr 1,65 Zr 1,3 Ta 1,7 O9, Li 2x-y Sr 1-x Ta y Zr1-y O3 (where x = 0.75 y and 0.60 < y < 0.75), Li 3 / 8 Sr 7 / 16 Note 3 / 4 Zr 1 / 4 O3, Li 3x La (2 / 3-x) TiO3 (where 0 < x < 0.25) and combinations thereof.

[0050] In various aspects, the polymer-based particles may contain one or more polymer-based materials selected from the following group: polyethylene glycol, polyethylene oxide (PEO), poly(p-phenylene oxide) (PPO), poly(methyl methacrylate) (PMMA), polyacrylonitrile (PAN), polyvinylidene fluoride (PVDF), polyvinylidene fluoride-co-hexafluoropropylene (PVDF-HFP), polyvinyl chloride (PVC), and combinations thereof. The sulfide-based particles may contain one or more sulfide-based materials selected from the following group: Li₂S-P₂S₅, Li₂S-P₂S₅-MS. x (where M is Si, Ge and Sn and 0 ≤ x ≤ 2), Li 3,4 Si 0,4 P 0,6 S4, Li 10 GeP2S 11,7 O 0,3 , Li 9,6 P3S12 , Li7P3S 11 , Li9P3S9O3, Li 10,35 Si 1,35 P 1,65 S 12 , Li 9,81 Sn 0,81 P 2,19 S 12 , Li 10 (Si 0,5 Ge 0,5 )P2S 12 , Li(Ge 0,5 Sn 0,5 )P2S 12 , Li(Si 0,5 Sn 0,5 )P S S 12 , Li 10 GeP2S 12 (LGPS), Li6PS5X (where X is Cl, Br or I), Li7P2S8I, Li 10,35 Ge 1,35 P 1,65 S 12 , Li 3,25 Ge 0,25 P 0,75 S4, Li 10 SnP2S 12 , Li 10 SiP2S 12 , Li 9,54 Si 1,74 P 1,44 S 11,7 Cl 10,3 , (1-x)P2S5-xLi2S (where 0.5 ≤ x ≤ 0.7) and combinations thereof. The halide-based particles can contain one or more halide-based materials selected from the group consisting of: Li2CdCl4, Li2MgCl4, Li2Cdl4, Li2ZnI4, Li3OCl, Li5ZnI4, Li3OCl 1-x Br x(where 0 < x < 1) and combinations thereof.

[0051] In various aspects, the borate-based particles can contain one or more borate-based materials selected from the group consisting of: Li₂B₄O₇, Li₂O-(B₂O₃)-(P₂O₅), and combinations thereof. The nitride-based particles can contain one or more nitride-based materials selected from the group consisting of: Li₃N, Li₇PN₄, LiSi₂N₃, LiPON, and combinations thereof. The hydride-based particles can contain one or more hydride-based materials selected from the group consisting of: Li₃AlH₆, LiBH₄, LiBH₄-LiX (where X is one of Cl, Br, and I), LiNH₂, Li₂NH, LiBH₄-LiNH₂, and combinations thereof. In further variations, electrolyte 30 can be a quasi-solid electrolyte comprising a hybrid of the non-aqueous liquid electrolyte solution described above and solid-state electrolyte systems—e.g.,with one or more ionic liquids and one or more metal oxide particles, such as aluminum oxide (Al2O3) and / or silicon dioxide (SiO2).

[0052] In various aspects, for example, if the electrolyte 30 is a non-aqueous liquid electrolyte solution, the separator 26 can be a microporous polymeric separator containing, for example, a polyolefin. The polyolefin can be a homopolymer (derived from a single monomer component) or a heteropolymer (derived from more than one monomer component), which can be either linear or branched. If a heteropolymer is derived from two monomer components, the polyolefin can adopt any copolymer chain arrangement, including that of a block copolymer or a statistical copolymer. Similarly, if the polyolefin is a heteropolymer derived from more than two monomer components, it can also be a block copolymer or a statistical copolymer.In certain aspects, the polyolefin can be polyethylene (PE), polypropylene (PP), or a mixture of PE and PP, or multilayer structured porous films made of PE and / or PP. CELGARD is one example of a commercially available porous membrane. ® 2500 (a single-layer polypropylene separator) and CELGARD ® 2320 (a three-layer polypropylene / polyethylene / polypropylene separator) is available from Celgard LLC. Various other conventionally available polymers and commercial products for the manufacture of separator 26 are considered, as are the many manufacturing processes that can be employed to produce such a microporous polymer separator 26.

[0053] If the separator 26 is a microporous polymeric separator, it can be a single layer or a multilayer laminate, which can be produced using either a dry or wet process. For example, in certain cases, a single layer of the polyolefin can constitute the entire separator 26. In other cases, the separator 26 can be a fibrous membrane with numerous pores extending between the opposing surfaces and having a thickness of, for example, less than one millimeter. Alternatively, several discrete layers of similar or dissimilar polyolefins can be assembled to form the separator 26.

[0054] Separator 26 can contain other polymers besides polyolefin, such as polyethylene terephthalate (PET), polyvinylidene fluoride (PVdF), polyamide (Ny ions), polyurethanes, polycarbonates, polyesters, polyetheretherketones (PEEK), polyethersulfones (PES), polyimides (PI), polyamideimides, polyethers, polyoxymethylene (e.g., acetal), polybutylene terephthalate, polyethylene naphthenate, polybutene, polymethylpentene, polyolefin copolymers, acrylonitrile butadiene styrene copolymers (ABS), polystyrene copolymers, polymethyl methacrylate (PMMA), polysiloxane polymers (e.g., polydimethylsiloxane (PDMS)), polybenzimidazole (PBI), polybenzoxazole (PBO), polyphenylenes, polyarylene etherketones, polyperfluorocyclobutanes, and polyvinylidene fluoride copolymers (e.g., PVdF-hexafluoropropylene). (PVdF-HFP)), polyvinylidene fluoride terpolymers, polyvinyl fluoride, liquid crystalline polymers (e.g.VECTRAN™ (Hoechst AG, Germany) and ZENITE® (DuPont, Wilmington, Germany), polyaramides, polyphenylene oxide, cellulose materials, mesoporous silicon dioxide, or any other material suitable for creating the required porous structure. The polyolefin layer and any other optional polymer layers can also be incorporated as a fiber layer into the separator 26 to help impart suitable structural and porosity properties to the separator 26.

[0055] In certain aspects, the separator 26 may also include one or more ceramic coating layers and a coating of heat-resistant material. The ceramic coating layer and / or the coating of heat-resistant material may be arranged on one or more sides of the separator 26. The material forming the ceramic layer may be selected from the group consisting of: aluminum oxide (Al₂O₃), silicon dioxide (SiO₂), titanium dioxide (TiO₂), and combinations thereof. The heat-resistant material may be selected from the group consisting of: Nomex, aramid, and combinations thereof.

[0056] The positive electrode 24 contains, in various aspects, a positive electroactive lithium-based material capable of undergoing lithium insertion and removal, alloying and peeling, or plating and stripping while functioning as the positive terminal of the capacitor bank 20. In various aspects, the positive electrode 24 can be formed by a variety of electroactive material particles (not shown). Such positive electroactive material particles can be arranged in one or more layers to define the three-dimensional structure of the positive electrode 24. In certain variations, the positive electrode 24 can additionally contain the electrolyte 30, e.g., a variety of electrolyte particles (not shown).

[0057] In various aspects, the positive electrode 24 can be a layered oxide cathode, a spinel cathode, or a polyanion cathode. For example, layered oxide cathodes (e.g., rock salt layered oxides) comprise one or more positive electroactive lithium-based materials selected from LiNi. x Mn y CO 1-x-y O2 (where 0 ≤ x ≤ 1 and 0 ≤ y ≤ 1), LiNi x Mn 1-x O2 (where 0 ≤ x ≤ 1), Li 1+x MO2 (where M is one of Mn, Ni, Co and Al and 0 ≤ x ≤ 1) (e.g. LiCoO2 (LCO), LiNiO2, LiMnO2, LiNi 0,5 Mn 0,5 O2, NMC111, NMC523, NMC622, NMC721, NMC811, NCA). Spinel cathodes comprise one or more positive electroactive lithium-based materials selected from LiMn2O4 and LiNi. 0,5 Mn 1,5O4. Olivine-type cathodes comprise one or more positive lithium-based electroactive materials such as LiV₂(PO₄)₃, LiFePO₄, LiCoPO₄, and LiMnPO₄. Tavorite-type cathodes include, for example, LiVPO₄F. Borate-type cathodes include, for example, one or more LiFeBO₃, LiCoBO₃, and LiMnBO₃. Silicate-type cathodes include, for example, Li₂FeSiO₄, Li₂MnSiO₄, and LiMnSiO₄F. In further variations, the positive electrode 24 can contain one or more other positive electroactive materials, such as one or more dilithium (2,5-dilithiooxy) terephthalate and polyimide. Optionally, the positive electroactive material can be coated (e.g., with LiNbO₃ and / or Al₂O₃) and / or doped (e.g., with one or more magnesium (Mg), aluminum (Al), and manganese (Mn)).

[0058] The positive electroactive material of the positive electrode 24 can optionally be mixed with one or more electrically conductive materials that provide an electron-conducting path and / or at least one polymeric binder material that improves the structural integrity of the positive electrode 24. For example, the positive electroactive material in the positive electrode 24 can optionally be mixed with binders such as poly(tetrafluoroethylene) (PTFE), sodium carboxymethylcellulose (CMC), styrene-butadiene rubber (SBR), polyvinylidene fluoride (PVDF), nitrile butadiene rubber (NBR), styrene-ethylene-butylene-styrene copolymer (SEBS), styrene-butadiene-styrene copolymer (SBS), lithium polyacrylate (LiPAA), sodium polyacrylate (NaPAA), sodium alginate, lithium alginate, ethylene propylene diene monomer (EPDM), and combinations thereof.Electrically conductive materials can include carbon-based materials, nickel powder or other metal particles, or conductive polymers. Carbon-based materials can contain, for example, particles of carbon black, graphite, carbon black (such as KETCHEN™ or DENKA™), carbon fibers and nanotubes, graphene, and similar materials. Examples of conductive polymers include polyaniline, polythiophene, polyacetylene, polypyrrole, and the like.

[0059] For example, the positive electrode 24 may contain more than or equal to approximately 50 wt.% to less than or equal to approximately 99 wt.%, and in certain aspects optionally more than or equal to approximately 50 wt.% to less than or equal to approximately 95 wt.%, of the positive electroactive material; more than or equal to approximately 0 wt.% to less than or equal to approximately 30 wt.%, and in certain aspects optionally more than or equal to approximately 2 wt.% to less than or equal to approximately 5 wt.% of one or more electrically conductive materials; and more than or equal to approximately 0 wt.% to less than or equal to approximately 20 wt.%, and in certain aspects optionally more than or equal to approximately 2 wt.% to less than or equal to approximately 5 wt.%, of one or more binders.

[0060] The negative electrode 22 contains a lithium host material in various aspects, capable of functioning as the negative terminal of a lithium-ion battery. For example, the negative electrode 22 can contain a lithium host material (e.g., a negative electroactive material) that can function as the negative terminal of the battery 20. In various aspects, the negative electrode 22 can be defined by a variety of negative electroactive material particles (not shown). Such negative electroactive material particles can be arranged in one or more layers to define the three-dimensional structure of the negative electrode 22. In certain variations, as noted above, the negative electrode 22 can additionally contain the electrolyte 30, for example, a variety of electrolyte particles (not shown).

[0061] The negative electrode 22 can contain a negative electroactive material based on lithium, comprising, for example, a lithium metal and / or a lithium alloy. In other variations, the negative electrode 22 can contain a negative electroactive material based on silicon, comprising, for example, silicon, a silicon alloy, silicon oxide, or combinations thereof, and in certain cases may be further mixed with graphite. In still other variations, the negative electrode 22 can be a negative electroactive material that is a carbon-containing anode, comprising, for example, one or more negative electroactive materials such as graphite, graphene, and / or carbon nanotubes (CNTs). In yet other variations, the negative electrode 22 can contain one or more lithium-accumulating negative electroactive materials, such as lithium titanium oxide (Li₄Ti₅O₆). 12), one or more transition metals (such as tin (Sn)), one or more metal oxides (such as vanadium oxide (V2O5), tin oxide (SnO), titanium dioxide (TiO2)), titanium-niobium oxide (Ti x Note y O z , where 0 ≤ x ≤ 2, 0 ≤ y ≤ 24 and 0 ≤ z ≤ 64) and include one or more metal sulfides (such as iron or iron sulfide (FeS)). In various aspects, as further explained below, the negatively electroactive material may be pre-lithitated.

[0062] In various aspects, the negative electroactive material in the negative electrode 22 can optionally be mixed with one or more electrically conductive materials that provide an electron-conducting path, and / or at least one polymeric binder material that improves the structural integrity of the negative electrode 22. For example, the negative electroactive material in the negative electrode 22 can optionally be mixed with binders such as poly(tetrafluoroethylene) (PTFE), sodium carboxymethylcellulose (CMC), styrene-butadiene rubber (SBR), polyvinylidene fluoride (PVDF), nitrile butadiene rubber (NBR), styrene-ethylene-butylene-styrene copolymer (SEBS), styrene-butadiene-styrene copolymer (SBS), lithium polyacrylate (LiPAA), sodium polyacrylate (NaPAA), sodium alginate, lithium alginate, and combinations thereof.Electrically conductive materials can include carbon-based materials, nickel powder or other metal particles, or conductive polymers. Carbon-based materials can contain, for example, particles of carbon black, graphite, carbon black (such as KETCHEN™ or DENKA™), carbon fibers and nanotubes, graphene, and similar materials. Examples of conductive polymers include polyaniline, polythiophene, polyacetylene, polypyrrole, and the like.

[0063] For example, the negative electrode 22 may contain more than or equal to approximately 50 wt.% to less than or equal to approximately 99 wt.%, and in certain aspects optionally more than or equal to approximately 50 wt.% to less than or equal to approximately 95 wt.%, of the negative electroactive material; more than or equal to approximately 0 wt.% to less than or equal to approximately 30 wt.%, and in certain aspects optionally more than or equal to approximately 5 wt.% to less than or equal to approximately 20 wt.% of one or more electrically conductive materials; and more than or equal to approximately 0 wt.% to less than or equal to approximately 20 wt.%, and in certain aspects optionally more than or equal to approximately 5 wt.% to less than or equal to approximately 15 wt.%, of one or more binders.

[0064] As described in more detail above, the negative electrode 22 can contain a comparatively high concentration of stored lithium during discharge, which is oxidized to lithium ions and electrons. Lithium ions can migrate from the negative electrode 22 to the positive electrode 24, for example, through the ionically conductive electrolyte 30 contained in the pores of an intervening porous separator 26. Simultaneously, the electrons traverse an external circuit 40 from the negative electrode 22 to the positive electrode 24. Such lithium ions can be incorporated into the material of the positive electrode 24 by an electrochemical reduction reaction. After a partial or complete discharge of its available capacity, the battery can be recharged or regenerated by an external power source, thereby reversing the electrochemical reactions that took place during discharge.

[0065] In various cases where electrochemical cells contain silicon, some of the stored lithium remains at the negative electrode 22 after a first cycle, e.g., due to the formation of a solid electrolyte interface (SEI) layer (not shown) on the negative electrode 22 during the first cycle, and e.g., due to ongoing lithium loss resulting from a rupture of the continuous solid electrolyte interface. For example, electrochemical cells with negative electrodes containing silicon can exhibit a capacity loss in the first cycle of more than about 20% and in certain aspects of about 40%. Similarly, electrochemical cells with negative electrodes containing silicon or silicon oxides (SiO₂) can also exhibit this. x) contains, a capacity loss of approximately 40% may occur in the first cycle. Such capacity losses in the first cycle create situations with low energy densities. This permanent loss of lithium ions can lead to a reduced specific energy and power in the battery 20, e.g., due to additional positive electrode mass that does not participate in the reversible operation of the battery.

[0066] In various aspects, the present disclosure provides a continuous process for the production of electroactive materials, e.g., electroactive materials for the applications in Fig. 1. Negative electrode shown. 22. The method involves contacting an electroactive material and an electrolyte containing a lithium-based salt, such that the electroactive material is dispersed in the electrolyte. As shown in Fig. As shown in Figure 2, the process can, for example, involve introducing a precursor for electroactive material, e.g., a plurality of electroactive particles 220, into a first container or vessel 230 which contains or carries a first electrolyte 210. The first container 230 is dimensioned such that the space velocity allows the lithiation of the electroactive material, e.g., Li 4,4x Si (where 0.05 ≤ x ≤ 0.8). The first container 230 is non-reactive with the first electrolyte 210 and its contents. The container 230 can be made of, for example, stainless steel, nickel, and / or copper.

[0067] In various aspects, the electroactive particles 220 can be, for example, a silicon powder made of silicon (Si) and / or silicon oxide (SiO₂). x, where 0 ≤ x ≤ 2) or comprise a tin powder containing tin (Sn). In some cases, the electroactive particles 220 may contain one or more coatings, e.g., a carbon coating and / or an aluminum oxide coating. In certain aspects, the process may involve pretreatment of the electroactive particles 220, e.g., using plasma processes to remove surface oxides, e.g., silicon oxides (SiO₂). x ), which are less reactive with lithium and lithium ions (Li + ) are, as well as to improve mechanical and surface stabilization. The electroactive particles 220 can have a first average diameter greater than or equal to approximately 10 nm to less than or equal to approximately 10 µm, greater than or equal to approximately 1 µm to less than or equal to approximately 5 µm, and optionally approximately 3 µm in certain aspects.

[0068] The first electrolyte 210 may contain one or more lithium salts selected from the group consisting of: lithium hexafluorophosphate (LiPF6), lithium perchlorate (LiClO4), lithium tetrachloroaluminate (LiAlCl4), lithium iodide (Lil), lithium bromide (LiBr), lithium thiocyanate (LiSCN), lithium tetrafluoroborate (LiBF4), lithium difluorooxalatoborate (LiBF2(C2O4)) (LiODFB), lithium tetraphenylborate (LiB(C6H5)4), lithium bis(oxalate)borate (LiB(C2O4)2) (LiBOB), lithium tetrafluorooxalatophosphate (LiPF4(C2O4)) (LiFOP), lithium nitrate (LiNO3), lithium hexafluoroarsenate (LiAsF6), lithium trifluoromethanesulfonate (LiCF3SO3), lithium bis(trifluoromethanesulfonimide) (LiTFSI) (LiN(CF3SO2)2), lithium fluorosulfonylimide (LiN(FSO2)2) (LiFSI), lithium fluoroalkyl phosphate (LiFAP) (Li3O4P) and combinations thereof, and a solvent mixture containing one or more different alkyl carbonates, such as cyclic carbonates (e.g.Ethylene carbonate (EC), propylene conoxidate (PC), butylene conoxidate (BC), fluoroethylene conoxidate (FEC)), linear carbonates (e.g. dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate, methyl propionate), γ-lactones (e.g. γ-butyrolactone, γ-valerolactone), chain structure ethers (e.g. 1,2-dimethoxyethane (DME), 1,2-diethoxyethane, ethoxymethoxyethane), cyclic ethers (e.g. tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane (DOL)), sulfur compounds (e.g. sulfolane) and combinations thereof.

[0069] The process may further include the introduction of a lithium 240 source. In certain aspects, the lithium 240 source may have a surface area, e.g., greater than or equal to approximately 0.01 cm². 2 Lithium source / 1 mg precursor of the electroactive material to less than or equal to approximately 1 cm 2 Lithium source / 1 mg precursor of the electroactive material, and in certain aspects optionally greater than or equal to approximately 0.1 cm 2Lithium source / 1 mg precursor of the electroactive material to less than or equal to approximately 1 cm 2 Lithium source / 1 mg precursor of the electroactive material. The required surface area of ​​the lithium source 240 may depend in certain aspects on the formulation of the electrolyte 210, as well as on the geometry of the container 230 and the chosen precursor for electroactive material, to give a non-limiting example. In various aspects, the lithium source 240 may, for example, contain solid lithium in the form of lithium-coated mesh and / or foam, plates, rods, sheets, strips, chunks, powders, granules, other coatings, and / or other forms. In certain aspects, as shown, an optional electron path 242 may also connect the lithium source 240 and the first electrolyte 210.

[0070] Upon contact with the first electrolyte 210, which can be at room temperature (e.g., a temperature greater than or equal to approximately 20 °C to less than or equal to approximately 25 °C, and optionally approximately 21 °C in certain aspects), the lithium source 240 ionizes. For example, lithium has a comparatively low redox potential, for instance, approximately -3.04 V compared to the standard hydrogen electrode (“SHE”). Potential differences between the lithium and the electroactive material of the electroactive particles 220 cause electrons (e - ) from the lithium source 240 to the electroactive particles 220, so that lithium ions (Li + ) are released into the first electrolyte 210 as a means of charge balancing. Charge neutrality is achieved when the lithium ions (Li +) upon contact with the electroactive particles 220, follow the electrons and spontaneously (Δ42 kJ / mol) form a fully lithiated electroactive material, which is considered the first state, e.g. Li 4,4x Si, where 0.75 ≤ x ≤ 1, defines the first or fully lithiated electroactive particle 222. The first lithiated electroactive particles 222 can have a first lithiation state of more than or equal to about 70%, more than or equal to about 80%, and in certain aspects more than or equal to about 90% of the total lithiation. In various aspects, the first lithiated electroactive particles 222 can have a second average particle diameter of more than or equal to about 10 nm to less than or equal to about 30 µm, and in certain aspects optionally greater than or equal to about 1 µm to less than or equal to about 10 µm.

[0071] The reaction of lithium ions (Li +The interaction of the electroactive particles 220 and the lithium source 240 can occur in certain aspects, for example, if the first container 230 has a surface area much larger than that of the lithium source, and if the electroactive particles 220 come into contact with a grounded or soil surface, for example, on or with an internal surface of the first container 230, in order to obtain electrons, for example, electrons left over after lithium ionization. In other cases, lithium sources with larger surface areas can have faster reaction rates because the probability of collision and contact between the electroactive particles 220 and the lithium source 240 and / or lithium ions is greater. In certain cases, for example, lithium ions can be plated onto one or more exposed surfaces of the first container 230, for example, by electrically connecting the lithium source 240 and one or more exposed surfaces of the first container 230.Such plating can further increase the available surface area of ​​the lithium ions and thus the reaction rate.

[0072] Once complete lithiation is achieved, the process may further include a partial electrochemical discharge (e.g., reduction of the lithium content) of the first lithiated electroactive particles 222 to obtain optimal lithiation conditions, e.g., about 40%, about 30%, and in certain aspects optionally about 20% of the total amount of lithium present in the electroactive material in the first or complete lithiation state, as represented by the second lithiated electroactive particles 224. For example, in certain cases, the first lithiated electroactive particles 222 may comprise silicon, and the first or complete state may be represented by Li 4,4xSi can be denoted, where 0.75 ≤ x ≤ 1. The second or optimized state of the second lithiated electroactive particle 224 can be described by Li 4,4x Si are to be denoted, where 0.015 ≤ x ≤ 0.5, including as Li 0,8 Yes.

[0073] For example, in certain variations, the first lithiated electroactive particles 222 in the first state can be replaced by Li 3,3 Si (with x = 0.75), and the second lithiated electroactive particles 224 in the second state, which have about 40% of the amount of lithium present compared to the first lithiated electroactive particles 22, can be replaced by Li 1,32 Si can be designated; the second lithiated electroactive particles 224 in the second state, which have about 30% of the amount of lithium present compared to the first lithiated electroactive particles 22, can be replaced by Li 0,99Si; and the second lithiated electroactive particles 224 in the second state, which have about 20% of the amount of lithium present compared to the first lithiated electroactive particles 22, can be replaced by Li 0,66 They are called Si.

[0074] According to Fig. 2. The fully lithiated electroactive particles 222, as shown, can travel or migrate from the first container 230 to a second container 250 through a continuous process. The second container 250 can contain or carry a second electrolyte 260. Like the first container 230, the second container 250 can also comprise one or more materials that are non-reactive with the second electrolyte 260 and its contents. The second container 250 can, for example, be made of stainless steel, nickel, and / or copper.

[0075] The second electrolyte 260 can be the same or different from the first electrolyte 210.In various aspects, the second electrolyte 260, for example, may contain one or more lithium salts selected from the group consisting of: lithium hexafluorophosphate (LiPF6); Lithium perchlorate (LiClO4), lithium tetrachloroaluminate (LiAlCl4), lithium iodide (Lil), lithium bromide (LiBr), lithium thiocyanate (LiSCN), lithium tetrafluoroborate (LiBF4), lithium difluorooxalatoborate (LiBF2(C2O4)) (LiODFB), lithium tetraphenylborate (LiB(C6H5)4), lithium bis(oxalate)borate (LiB(C2O4)2) (LiBOB), lithium tetrafluorooxalatophosphate (LiPF4(C2O4)) (LiFOP), lithium nitrate (LiNO3), lithium hexafluoroarsenate (LiAsF6), lithium trifluoromethanesulfonate (LiCF3SO3), lithium bis(trifluoromethanesulfonimide) (LiTFSI) (LiN(CF3SO2)2), lithium fluorosulfonylimide (LiN(FSO2)2) (LiFSI), lithium fluoroalkylphosphate (LiFAP) (Li3O4P) and combinations thereof, and a solvent mixture containing one or more different alkyl carbonates, such as cyclic carbonates (e.g.Ethylene carbonate (EC), propylene conoxidate (PC), butylene conoxidate (BC), fluoroethylene conoxidate (FEC)), linear carbonates (e.g. dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate, methyl propionate), γ-lactones (e.g. γ-butyrolactone, γ-valerolactone), chain structure ethers (e.g. 1,2-dimethoxyethane (DME), 1,2-diethoxyethane, ethoxymethoxyethane), cyclic ethers (e.g. tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane (DOL)), sulfur compounds (e.g. sulfolane) and combinations thereof.

[0076] A counter electrode 270 is arranged inside the second container 250. Like the containers 230 and 250, the counter electrode 270 can contain a non-reactive metal, and the electrochemical process can be driven by an applied external voltage. In certain other aspects, the counter electrode 270 can contain, for example, graphite, lithium phosphate (Li3PO4) (LPO), and / or lithium titanate (Li2TiO3) (LTO). In various aspects, the counter electrode includes a separator 272, for example, a porous frit that coats one or more surfaces of the counter electrode 270 or forms a sleeve or pocket that receives the counter electrode 270. The separator 272 prevents contact between the counter electrode 270 and the fully lithiated electroactive particles 222 in a first state and / or optimized lithiated electroactive particles 224 in a second state.The separator 272 can be porous, for example in the form of a porous frit with a porosity ranging from approximately 20 vol.% to approximately 99.9 vol.%, and optionally, in certain aspects, from approximately 25 vol.% to approximately 75 vol.%. The pores have an average size that is smaller than the average particle diameters of the fully lithiated electroactive particles 222 in a first state and / or the optimized lithiated electroactive particles 224 in a second state.

[0077] The process involves applying a bias voltage to the counter electrode 270. The bias voltage can cause lithium ions (Li) to be generated. + ) from the fully lithiated electroactive particles 222 to the counter electrode 270 (e.g. Li 4,4 Si → Li 0,8 Si + 3.6 Li + + 3.6 e -) to form an optimized lithiated electroactive material that defines an optimized lithiated electroactive particle 224.

[0078] The applied voltage can depend in certain aspects on the chosen precursor for electroactive material as well as on the design of the containers 230, 250, and various other production steps. For example, in certain aspects, a voltage greater than or equal to approximately 0.1 V to less than or equal to approximately 24 V, and optionally greater than or equal to approximately 0.5 V to less than or equal to approximately 10 V, can be applied for a duration of greater than or equal to approximately 1 minute to less than or equal to approximately 24 hours, and optionally greater than or equal to approximately 5 minutes to less than or equal to approximately 10 minutes. The optimized lithiated electroactive particle 224 in a second state can have a third average particle diameter of greater than or equal to approximately 10 nm to less than or equal to approximately 30 µm, and optionally greater than or equal to approximately 1 µm to less than or equal to approximately 10 µm.

[0079] In certain variations, the process includes the recovery of the discharged lithium for reuse (e.g. 3.6 Li + + 3.6 e - → 3.6 Li 0 For example, the lithium plated on the counter electrode 270 can be used as a lithium source 240 in subsequent lithiation processes by moving the lithium-coated counter electrode 270 from the second container 250 to a first container 230. The process further includes the isolation or separation of the optimized lithiated electroactive particle 224 in a second state for use in a negative electrode, for example, the one in Fig. The optimized lithiated electroactive particle 224 can be separated by known filtration and / or centrifugation methods. In certain variations, the method also includes coating the optimized lithiated electroactive particle 224 to increase its mechanical stability. For example, after exiting the second container 250, the optimized lithiated electroactive particle 224 can be coated with an aluminum oxide (Al₂O₃) layer having a thickness greater than or equal to about 3 nm to less than or equal to about 1 µm, and optionally greater than or equal to about 0.1 nm to less than or equal to about 0.5 µm in certain aspects. To give a non-limiting example, the optimized lithiated electroactive particle 224 can also be coated using an atomic layer deposition (“ALD”) process.

[0080] In several other aspects, the present disclosure provides a channel flow process for the production of electroactive materials, for example, electroactive materials for the use in Fig. 1. Negative electrode shown. 22. The method involves moving particles of electroactive material through a flow channel containing a lithium source, e.g., lithium metal. As shown in Fig. As shown in Figure 3, the method may, for example, involve introducing a precursor for electroactive material, such as a plurality of electroactive particles 320, into a flow channel 330 which contains or carries an electrolyte 310.

[0081] The flow channel 330 can be defined by or formed from a lithium source 340, e.g., solid lithium selected in the form of lithium-coated fabrics and / or foam, plates, rods, films, tapes, chunks, powders, granules, other coatings, and / or other forms. In various other cases not shown here, it is clear to those skilled in the art that the lithium source 340 can, for example, be arranged as a coating or layer on exposed surfaces of a substrate that defines the flow channel 330. In still other variations not shown, it is clear to those skilled in the art that the lithium source 340 can be arranged within the flow channel 330.The electroactive particles 320 can have a first average diameter greater than or equal to approximately 10 nm to less than or equal to approximately 10 µm, greater than or equal to approximately 1 µm to less than or equal to approximately 5 µm, and optionally approximately 3 µm in certain aspects. In various aspects, the electroactive particles 320 can, for example, consist of a silicon powder. In certain aspects, the process can include a pretreatment of the electroactive particles 320, for example, using plasma processes to remove surface oxides, such as silicon oxides (SiO₂). x ), to remove the kinetics of the electroactive particles 320 both during the lithiation process and during subsequent use in an electrochemical cell, for example the one in Fig. 1 shown battery 20, to improve.

[0082] Electrolyte 310 may contain one or more lithium salts selected from the group consisting of: lithium hexafluorophosphate (LiPF6), lithium perchlorate (LiClO4), lithium tetrachloroaluminate (LiAlCl4), lithium iodide (Lil), lithium bromide (LiBr), lithium thiocyanate (LiSCN), lithium tetrafluoroborate (LiBF4), lithium difluorooxalatoborate (LiBF2(C2O4)) (LiODFB), lithium tetraphenylborate (LiB(C6H5)4), lithium bis(oxalate)borate (LiB(C2O4)2) (LiBOB), lithium tetrafluorooxalatophosphate (LiPF4(C2O4)) (LiFOP), lithium nitrate (LiNO3), lithium hexafluoroarsenate (LiAsF6), lithium trifluoromethanesulfonate (LiCF3SO3), lithium bis(trifluoromethanesulfonimide) (LiTFSI) (LiN(CF3SO2)2), lithium fluorosulfonylimide (LiN(FSO2)2) (LiFSI), lithium fluoroalkyl phosphate (LiFAP) (Li3O4P) and combinations thereof, and a solvent mixture containing one or more different alkyl carbonates, such as cyclic carbonates (e.g.Ethylene carbonate (EC), propylene conoxidate (PC), butylene conoxidate (BC), fluoroethylene conoxidate (FEC)), linear carbonates (e.g. dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate, methyl propionate), γ-lactones (e.g. γ-butyrolactone, γ-valerolactone), chain structure ethers (e.g. 1,2-dimethoxyethane (DME), 1,2-diethoxyethane, ethoxymethoxyethane), cyclic ethers (e.g. tetrahydrofuran, 2-methyltetrahydrofuran, 1,3-dioxolane (DOL)), sulfur compounds (e.g. sulfolane) and combinations thereof.

[0083] When the electrolyte 310, which can be at room temperature, comes into contact with the lithium source 340, it ionizes. For example, lithium, as mentioned above, has a comparatively low redox potential, for example, about -3.04 V compared to the standard hydrogen electrode (“SHE”). Potential differences between the lithium and the electroactive material of the electroactive particles 320 cause electrons (e) to be drawn into the lithium. -) from the lithium source 340 to the electroactive particles 320, so that lithium ions (Li + ) are released into the electrolyte 310 as a means of charge balancing. Charge neutrality is achieved when the lithium ions (Li + ) upon contact with the electroactive particles 320, they follow the electrons and spontaneously form (Δ 42 kJ / mol) a completely lithiated electroactive material, e.g. Li 4,4x Si, where 0.75 ≤ x ≤ 1, defines the fully lithiated electroactive particle 322 in a first state. The fully lithiated electroactive particles 322 can have a second average particle diameter of greater than or equal to about 10 nm to less than or equal to about 30 µm, and in certain aspects optionally greater than or equal to about 1 µm to less than or equal to about 10 µm. The lithiation rate can be controlled by the flow rate of the electrolyte 310 and / or the length of the flow channel 330.

[0084] Once complete lithification is achieved, the process can be carried out in Fig. The methods described in section 3 further include a partial electrochemical discharge (e.g., reduction of the lithium content) of the fully lithiated electroactive particles 322 to obtain optimal lithiation conditions, e.g., about 40%, about 30%, and in certain aspects optionally about 20% of the total amount of lithium present in the electroactive material in the first or fully lithiated state, as by means of second lithiated electroactive particles 324 (e.g., Li 4,4x Si, where 0.015 ≤ x ≤ 0.5, as Li 0,8 Si). Optimized lithiated electroactive particles 324 in a second state can be formed by delthiation, which, using a counter electrode similar to that in Fig. The procedures shown in section 2 can be carried out.

Claims

[1] Method for producing a lithiated electroactive material, the method comprising: Dispersing a precursor for electroactive material (220, 320) in an electrolyte (210, 310) containing a lithium-based salt at room temperature to form an electrolyte mixture; Contacting the electrolyte mixture and a lithium source (240, 340) to cause the lithium source (240, 340) to ionize and release lithium ions (Li + to form lithium ions (Li + ) react with the precursor of the electroactive material (220, 320) in the electrolyte mixture to form the lithiated electroactive material; and where, after the reaction of the lithium ions (Li +) with the precursor for electroactive material (220, 320) in the electrolyte mixture the lithiated electroactive material is in a first state (222, 322), and the process further comprises the electrochemical discharge of the lithiated electroactive material to have less than or equal to 40% of the total lithium present in the lithiated electroactive material in the first state (222, 322); wherein the process for forming the lithiated electroactive material is a continuous process and the dispersion and contacting take place in a first container (230) and the electrochemical discharge in a second container (250), wherein the first and the second containers (230, 250) are formed of materials that are not reactive with the electrolyte mixture, and the first and second containers (230, 250) are in fluid communication and the lithiated electroactive material flows from the first container (230) to the second container (250); or wherein the lithium source (340) coats an inner channel (330) of a channel flow reactor and the electrolyte mixture migrates through the channel flow reactor; or wherein the lithium source (340) defines an internal surface of a channel flow reactor and the electrolyte mixture migrates through the channel flow reactor. [2] Method according to claim 1, wherein after the reaction of the lithium ions (Li + ) with the precursor of the electroactive material (220, 320) in the electrolyte mixture the lithiated electroactive material is in a first state (222, 322), which is described by the formula Li 4,4x Si is designated where 0.75 ≤ x ≤ 1, and the process further comprises the electrochemical discharge of the lithiated electroactive material to a second state (224, 324) which is designated by the formula Li 4,4x Si is denoted, where 0.015 ≤ x ≤ 0.

5. [3] Method according to claim 1, wherein the second container (250) contains a counter electrode (270) comprising one or more of graphite, lithium phosphate (Li3PO4) (LPO) and lithium titanate (Li2TiO3) (LTO), and the counter electrode (270) is arranged within a separator (272). [4] The method of claim 3, wherein the method comprises applying a bias voltage to the counter electrode (270), wherein, upon application of the bias voltage, discharged lithium ions (Li + ) move from the lithiated electroactive particles to the counter electrode (270) to form the lithiated electroactive material with the second state (224, 324), wherein the bias voltage is greater than or equal to 0.1 V to less than or equal to 24 V and the bias voltage is applied for more than or equal to 1 minute to less than or equal to 24 hours. [5] The method of claim 1, wherein the method further comprises isolating the lithiated electroactive material and, after electrochemical discharge, discharging the discharged lithium ions (Li + ) are recovered and returned.

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