Elemental metal and carbon mixtures for energy storage devices

Abstract

To provide energy storage devices and methods for fabricating the same.SOLUTION: An energy storage device includes a first electrode, a second electrode, and a separator between the first electrode and the second electrode where the first electrode or the second electrode includes elemental lithium metal 704 and carbon particles 702. A method for fabricating an energy storage device can include forming a first electrode and a second electrode, and inserting a separator between the first electrode and the second electrode, where forming the first electrode or the second electrode includes combining elemental lithium metal and a plurality of carbon particles.SELECTED DRAWING: Figure 7

Description

[Technical field]

[0001] The present invention generally relates to compositions for electrodes of energy storage devices, energy storage devices incorporating such electrodes, The present invention relates to an energy storage device, and related methods. [Background technology]

[0002] Lithium ions, sodium ions, potassium ions, magnesium ions and / or Energy storage devices based on lithium ion or aluminum ions provide power for a wide range of electrical devices. Batteries and / or or capacitors are used, for example, in wind power systems, uninterruptible power systems (UPS), photovoltaic Various applications, including power generation and / or energy recovery systems for industrial equipment and transportation systems The electrodes of such batteries and / or capacitors can be implemented in a variety of applications. During manufacturing, a pre-doping process may be performed. Summary of the Invention

[0003] In some embodiments, the energy storage device includes a first electrode, a second electrode, and a and a separator between the first electrode and the second electrode, and at least one of the first electrode and the second electrode is made of carbon particles. The elemental metal may include elemental lithium gold. elemental lithium metal, consisting essentially of elemental lithium metal, or The elemental metal may comprise elemental sodium metal, essentially consisting of It can be composed of elemental sodium metal. The genus includes, consists essentially of, or consists of elemental potassium metal. Elemental metals include elemental magnesium metal and can consist essentially of elemental magnesium metal. It can be made of magnesium metal or it can be made of elemental magnesium metal. The genus includes, consists essentially of, or consists of elemental aluminum metal. It may be made of bare aluminum metal.

[0004] In some embodiments, at least one of the first electrode and the second electrode is elemental lithium The first electrode and the second electrode may include a dry electrode film containing metal and carbon particles. At least one of the two electrodes is a lithium-ion battery or a lithium-ion capacitor. It may include an anode, such as an anode.

[0005] In some embodiments, the carbon particles include porous carbon particles, each of which comprises a plurality of porous carbon particles. at least some of the pores are filled with at least some of the element lithium In some embodiments, the porous carbon particles include activated carbon. In some embodiments, the porous carbon particles include hierarchically structured carbon. In some embodiments, the porous carbon particles include mesoporous carbon. It is possible to do so.

[0006] In some embodiments, a solid electrolyte interface (SEI) covering the exposed portion of elemental lithium metal. This SEI layer can form a layer of the elements that are present beneath the outer surface of the corresponding porous carbon particle. The exposed portions of the lithium metal can be covered.

[0007] In some embodiments, the carbon particles include graphite particles.

[0008] In some embodiments, the elemental lithium metal can include elemental lithium metal particles. Cut.

[0009] In some embodiments, the method of manufacturing an energy storage device includes: forming a first electrode film mixture; and forming an electrode film from the composite.

[0010] In some embodiments, the method further comprises the step of: and forming a second electrode and inserting a separator between the first electrode and the second electrode. The method may further include a step of:

[0011] In some embodiments, the plurality of carbon particles can include a plurality of porous carbon particles; Each porous carbon particle has a plurality of pores. In some embodiments, the porous carbon particles In some embodiments, the porous carbon particles can include activated carbon. In some embodiments, the porous carbon particles can include mesoporous carbon. It may contain porous carbon.

[0012] In some embodiments, combining elemental lithium metal and a plurality of carbon particles. At least some of the pores corresponding to each porous carbon particle are formed from at least some of the original material. The elemental lithium metal and a plurality of porous carbon particles are mixed to receive the elemental lithium metal. The method may include a step of combining the above-mentioned components.

[0013] In some embodiments, a solid electrolyte interface (SEI) layer is applied to the exposed portion of the elemental lithium metal. The step of forming the SEI layer can be performed by forming a layer on the outer surface of the corresponding porous carbon particle. In some embodiments, the method may include covering the exposed portions of the elemental lithium metal. The step of forming the SEI layer includes exposing the exposed portion of the elemental lithium metal to an electrolyte solvent vapor. In some embodiments, the exposed portion of the elemental lithium is exposed to an electrolyte solvent vapor. The step of subjecting the exposed portion of the elemental lithium to carbonate vapor.

[0014] In some embodiments, the plurality of carbon particles comprises a plurality of graphite particles.

[0015] In some embodiments, the mixture is a substantially homogeneous mixture.

[0016] In some embodiments, bulk elemental lithium metal is The process of producing the bulk elemental lithium metal and reducing the size of the bulk elemental lithium metal to multiple elemental lithium and forming aluminum metal particles.

[0017] In some embodiments, the step of combining elemental lithium metal with a plurality of carbon particles comprises , dry elemental lithium metal is mixed with a plurality of dry carbon particles to form a dry electrode film mixture In some embodiments, the step of forming at least one of the first electrode and the second electrode includes forming a first electrode. One includes the anode of a lithium-ion battery or lithium-ion capacitor.

[0018] In some embodiments, bulk materials for forming lithium ion energy storage devices The mixture may contain elemental lithium metal and activated carbon particles.

[0019] In some embodiments, a bulk mixture comprising elemental lithium metal and activated carbon particles is A mixing device is provided having an interior volume for receiving the mixing device.

[0020] In some embodiments, the mixing device further comprises an inert gas within the interior volume. In some embodiments, the mixing device further includes an electrolyte solvent vapor within the chamber.

[0021] In some embodiments, the activated carbon particles comprise graphite. The activated carbon particles include porous carbon particles having elemental lithium metal intercalated within the pores.

[0022] In some embodiments, a pre-doped energy storage device electrode The energy storage device electrode is a mixture of elemental metals such as lithium and activated carbon particles. It may contain a mixture.

[0023] In some embodiments, an energy storage device is provided, wherein the energy storage The device combines elemental lithium metal with a plurality of carbon particles to form an electrode film mixture. and forming a first electrode film from the electrode film mixture. In a further embodiment, the energy storage device is manufactured between the first electrode and the second electrode. and optionally, inserting the first electrode, the separator, and the second electrode into a housing. and optionally further disposing an electrolyte within the housing, the first electrode and the second electrode. is contacted with the electrolyte and, optionally, a second electrode is pre-doped.

[0024] To summarize the present invention and the advantages it provides over the prior art, Certain objectives and advantages are set forth herein. Of course, such objectives and advantages are not necessarily limited to the present invention. It is to be understood that not all such improvements or advantages need be achieved in accordance with any particular embodiment. Thus, for example, one of skill in the art may be able to achieve or optimize an advantage or group of advantages. It is to be understood that the invention is not limited to the disclosed embodiments, and that the invention may be practiced in a manner that is consistent with the disclosed embodiments, without necessarily achieving other objects or advantages. It will be understood that the above may be implemented.

[0025] All of these embodiments are intended to be within the scope of the invention(s) disclosed herein. These and other embodiments will become apparent to those skilled in the art from the following detailed description taken in conjunction with the accompanying drawings. It will be readily apparent that the present invention is not limited to any particular disclosed embodiment. I can't.

[0026] These and other features, aspects, and advantages of the present specification are described in detail in conjunction with the drawings of specific embodiments. Although the present invention will be described in detail below, this is intended to illustrate specific embodiments and is not to be construed as limiting the present invention. This does not limit the following.

[0027] This specification contains at least one drawing executed in color. Copies of the drawings will be available from the Office upon request and payment of the necessary fee. ) provided by [Brief description of the drawings]

[0028] [Figure 1] FIG. 1 is a schematic cross-sectional view of an energy storage device according to an embodiment. [Figure 2A] FIG. 2 is a schematic diagram of a porous carbon particle with or without elemental lithium metal within the pores, according to one embodiment. [Figure 2B] FIG. 2B is a schematic diagram of a porous carbon particle at a higher magnification than FIG. 2A. [Figure 2C] FIG. 2 is a schematic diagram showing openings corresponding to hollow channels or pores in a porous carbon particle. [Figure 2D] FIG. 2 is a schematic diagram of hollow channels or pores within a porous carbon particle containing elemental lithium metal. [Figure 2E] FIG. 2 is a schematic diagram showing openings in the exterior surface of a porous carbon particle having elemental lithium metal. [Figure 2F] FIG. 2E is a schematic diagram showing an SEI layer on exposed lithium metal within the openings on the exterior surface of the porous carbon particle shown in FIG. 2D. [Diagram 3] FIG. 2 is a flow diagram of an example process for preparing a mixture containing carbon particles and elemental lithium metal. [Figure 4] FIG. 2 is a flow diagram of an example process for making a plurality of lithium-carbon composite particles. [Diagram 5] FIG. 2 is a flow diagram of an example process for preparing a mixture containing graphite particles and elemental lithium metal. [Figure 6] FIG. 1 is a flow diagram of an example process for producing an electrode film using one or more of the compositions described herein. [Figure 7] FIG. 1 is a schematic diagram of an example of an apparatus configured to combine elemental lithium metal and carbon particles according to one or more of the processes described herein. [Figure 8A] 1A-1C are photographs showing different stages in the process of forming an electrode film composite from bulk elemental lithium metal and graphite particles according to one embodiment. [Figure 8B] 8B is a photograph showing the next stage in the process of forming an electrode film composite from bulk elemental lithium metal and graphite particles, as shown in FIG. 8A. [Figure 8C] 8C is a photograph showing the next step in the process of forming an electrode film composite from bulk elemental lithium metal and graphite particles, as shown in FIG. 8B. [Figure 9A] 1 is a voltage curve showing the specific capacity performance of a coin cell including an electrode film formed according to an example. [Figure 9B]1 is a voltage curve showing the specific capacity performance of a coin cell including an electrode film formed according to an example. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0029] Although specific embodiments and examples are described below, those of ordinary skill in the art will appreciate that the present invention may be practiced in and / or modifications beyond those disclosed in the embodiments and / or uses. Accordingly, the scope of the invention disclosed herein is as follows: The invention should not be limited by the specific embodiments described.

[0030] Disclosed below are mixtures of materials, corresponding electrodes, energy storage devices, and related These are all embodiments relating to a method for producing elemental lithium metal as a bulk material. As used herein, elemental lithium metal refers to lithium in the zero oxidation state. The term refers to lithium metal. It is used in traditional energy storage devices, including rechargeable energy storage applications. In its use, elemental lithium metal is not used as a raw material. By dispersing elemental lithium metal in the composition of the biologically active material, an electrode with finely distributed However, it is highly reactive and may be explosive under certain manufacturing conditions. For example, in the manufacture of conventional wet energy storage devices, lithium elements Bulk liquids such as water and / or N-methylpyrrolidone in which the base metal is wet processed Do not use elemental lithium metal as it is highly reactive and may explode when exposed to Instead, conventional energy storage devices use coatings that are surface treated to provide stability. The lithium materials used are known to have a coating layer. These lithium materials , such as materials including lithium cation and carbonate based compositions, For example, conventional methods use FLC Lithium's SLMP brand of Stable Li These conventional materials include a coating of salt. Many of these are broken down to make contact with lithium in a secondary processing step, but this Electrodes made from these materials have lower energy density and more complex processing steps. The processing and construction of the materials used herein are based on bulk elemental lithium. This allows the use of aluminum metal, thereby increasing the energy density of the resulting energy storage device. This increases the degree of oxidation and, to some extent, reduces the possibility of undesirable reactions or explosions.

[0031] Pre-doped electrodes are produced by including elemental metals in the electrode active material mixture. While it is not intended that this be a limitation of the scope of the invention by theory, The lithium metal contained in the electrode film undergoes an oxidation-reduction reaction to produce free metal ions. It is believed that electrodes containing the elemental metals described herein are therefore in contact with an electrolyte. When the lithium metal atom is released, it can release an electron and subsequently form a metal cation for each lithium metal atom. The metal ions can diffuse to either electrode. For example, in an energy storage device Typical anode materials generally include one or more intercalated carbon components. This intercalation carbon component is a material in which certain metal ions, such as lithium ions, are intercalated. The electrodes may be selected to be tercalated. When the anode contains a metal ion, the metal ion is intercalated into one or more activated carbon components of the anode. In this regard, for example, the cathode material of a capacitor is generally It contains a carbon component that can adsorb metal ions, such as lithium ions. When contacted with metal ions, the metal ions may be adsorbed onto the surface of the cathode.

[0032] Thus, in some embodiments, the materials and methods presented herein provide for the pre- This can have the advantage of reducing the number of steps required for doping. When included in a film mixture, the separate pre-doping required for existing electrode films is The electrode film mixtures presented herein are composed of elemental metals and multiple carbons. It is possible to allow intimate contact between the particles. Thus, the pre-doping material source (which may be a source of metal ions, e.g., elemental metal or a metal ion solution) and a carbon-based electrode. No pre-doping step is required, which requires a separate electrical element to provide electrical contact between the electrodes. Instead, embodiments herein provide a method for dissolving metal oxides in a metal oxide layer upon contact with an electrolyte in an energy storage device. A pre-doped electrode film containing elemental metal particles that release elemental ions is used. The poles can be provided.

[0033] Elemental metals can be less expensive than metal salts suitable as pre-doping sources. The materials and methods presented herein allow for the fabrication of pre-doped electrodes without the use of metal salts. Additionally, the materials and methods presented herein are compatible with dry electrode manufacturing techniques and therefore This reduces the process inefficiencies associated with wet electrode manufacturing. In some embodiments, the materials and methods provided herein make the manufacture of pre-doped electrodes cost-effective. The energy storage devices described herein with respect to lithium can be The elemental metals and related concepts described herein may be implemented in other energy storage devices and other metals. It can be understood that this can be done.

[0034] Bulk elemental lithium metal is available in sheets, bars, rods, or other forms of elemental lithium metal. In some embodiments, the bulk elemental lithium metal can be provided in the form of Each is about 1 mm 3 ~ approx. 1m 3 Including about 1mm 3 one or more pieces of elemental lithium metal having a volume greater than In some embodiments, the bulk elemental lithium metal can be from about 10 μm to about 8 μm. 0 μm, or about 5 μm to about 100 μm, including about 50 μm to about 100 μm. It can also be a metal sheet. Bulk elemental lithium metal is made up of chunks of lithium in various shapes. Bulk elemental lithium metal can be further reduced in size to particulate form. and the like, for example, graphite particles, porous carbon particles and / or activated carbon particles. It can be mixed with carbon such as elementary particles to form electrodes for energy storage devices. In some embodiments, the elemental metal, e.g., lithium, is added to the powder. In a further embodiment, the elemental metal, e.g., lithium, is a metal as defined herein. 1. One or more of the process steps shown in FIG. 1, e.g., one or more of steps 300, 400, 500, or 600. The powder is then reduced in size to form an elemental metal powder.

[0035] As used herein, carbon particles include porous and / or non-porous carbon particles. It can refer to carbon particles of various sizes, such as graphite. In some embodiments, carbon The elementary particles have a cumulative particle diameter D of about 1 μm to about 20 μm. 50 In some embodiments, Then, the cumulative particle diameter D 50 can be from about 1 μm to about 15 μm, or from about 2 μm to about 10 μm.

[0036] As used herein, porous carbon particles are defined as particles having pores or hollow channels extending therethrough. In some embodiments, the porous carbon particles can refer to a variety of carbon materials having a , nanoporous carbon particles, microporous carbon particles, mesoporous carbon particles, and and / or macroporous carbon particles. The pores or hollow channels may be about 1n In some embodiments, the porous carbon particles can have a diameter of about 2 μm to about 3 μm. A diameter of about 2% to about 10% of the particle, including about 2% to about 5% or about 5% to about 10% of the particle's diameter. For example, the pores of a porous carbon particle may be formed by arranging the pores in the body of the carbon particle. About 10% of the volume of the carbon particles, including about 10% to about 60%, about 10% to about 50%, and about 10% to about 40% of the volume ~It can account for about 80%.

[0037] In some embodiments, the porous carbon particles can include activated carbon particles. In some embodiments, the porous carbon particles may include hierarchically structured carbon particles. In some embodiments, the porous carbon particles include structured carbon nanotubes, structured It may include carbon nanowires and / or structured carbon nanosheets. In some embodiments, the porous carbon particles can include graphene sheets. In some embodiments, the porous carbon particles may be surface-treated carbon particles. For example, The treated carbon particles may include one or more functional groups on one or more surfaces of the treated carbon. For example, one or more functional groups may be reduced in number by about 10 compared to an untreated carbon surface. The treated carbon has a hydrogen-containing functional group. The number of functional groups, nitrogen-containing functional groups, and / or oxygen-containing functional groups may be reduced. In some embodiments, the treated carbon material has a hydrogen content of less than about 1%, including less than about 0.5%. In some embodiments, the treated carbon material contains less than about 0.1% In some embodiments, the treated carbon material has less than about 0.5% nitrogen-containing functional groups. In some embodiments, the process has less than about 5%, including less than about 3%, of oxygen-containing functional groups. The treated carbon material has about 30% less hydrogen-containing functional groups than the untreated carbon material.

[0038] In one embodiment, the mixture for manufacturing an electrode of an energy storage device comprises a plurality of carbon particles. Some embodiments include a plurality of elemental lithium metal particles, and a plurality of elemental lithium metal particles. In embodiments, the mixture is a dry particle mixture. The electrode film for the storage device electrode comprises a plurality of carbon particles and elemental lithium metal and a binder. and one or more other electrode components. In some embodiments, the electrode comprises a plurality of carbon particles, elemental lithium metal, and one or more electrode components. The electrode film can be formed from the dry particle mixture by dry processing. As used herein, a dry process or dry mix is ​​one that is free of or does not contain any liquids or solvents. This refers to processes and mixtures that are substantially free of granules, e.g., dry processing to remove granules from dry particle mixtures. The electrode film formed from the liquid is substantially resistant to residues from such liquids and / or solvents. In some embodiments, for example, by forming a wet slurry solution, In some embodiments, a wet process is used to form the electrode film. may be the anode of a lithium ion battery or a lithium ion capacitor. For example, a lithium-ion battery or lithium-ion capacitor consists of a cathode, an anode, and a separator between the cathode and the anode, the anode comprising: The electrode film includes a plurality of carbon particles and elemental lithium metal. In some embodiments, the elemental metal is present in an amount of about 0.1%, about 0.3%, about 0.5% by weight of the electrode film mixture. , about 0.7% by weight, about 1% by weight, about 1.5% by weight, about 2% by weight, about 2.5% by weight, about 3% by weight, about 3.5 Weight%, approx. 4% by weight, approx. 4.5% by weight, approx. 5% by weight, approx. 6% by weight, approx. 7% by weight, approx. 8% by weight, approx. 9 % or about 10% by weight. In certain embodiments, the elemental metal comprises an electrode foil. It can comprise about 1% to about 5% by weight of the film mixture.

[0039] In some embodiments, the plurality of carbon particles and elemental lithium metal are For example, the lithium-carbon composite particles may include conductive porous carbon particles and and containing elemental lithium metal within the pores or hollow channels of the porous carbon particles. In some embodiments, the elemental lithium metal in the pores can be In some embodiments, the elemental lithium metal in the pores is resolidified elemental lithium metal. The porous carbon particles may be mesoporous carbon particles. In the embodiment, the porous carbon particles are activated carbon particles or hierarchically structured carbon particles. In some embodiments, the plurality of lithium-carbon composite particles may include at least Also, multiple porous carbon particles with some pores that accept some elemental lithium metal In some embodiments, the plurality of lithium-carbon composite particles comprises elemental lithium metal. The porous carbon particles include a plurality of porous carbon particles having filled or substantially filled pores. As described in more detail in, in some embodiments, a plurality of lithium-carbon composites are The particles are formed by subjecting porous carbon particles and elemental lithium metal particles to subatmospheric pressure and a chamber. In some embodiments, the mixture is prepared by combining the mixture at a temperature above room temperature. The porous carbon particles and elemental lithium metal particles are heated at near ambient temperatures and near atmospheric pressures. The porous carbon particles and elemental lithium particles can be mixed under atmospheric pressure. Under inert conditions, e.g. in a container such as a mixing vessel, while only exposed to an inert gas such as benzene In some cases, the lithium-carbon composite particles can be mixed in a single solution to form multiple lithium-carbon composite particles. In an embodiment, the step of mixing the porous carbon particles and the elemental lithium particles comprises mixing the porous carbon particles and exposing the elemental lithium particles to a carbonate vapor or a carbonate liquid. In some embodiments, the plurality of lithium-carbon composite particles may include a A solid electrolyte interface (SEI) layer on elemental lithium metal within the opening in the face. In the embodiment, the step of forming the SEI layer includes dissolving a plurality of lithium-carbon composite particles in carbonate vapor. For example, exposing exposed elemental lithium gold within the openings of the pores on the outer surface of the particle to The metal can react with carbonate vapor, thereby releasing its exposed elemental lithium. The SEI layer forms only on the metal or only on substantially exposed elemental lithium metal In a further embodiment, the SEI layer is made of ethylene carbonate (EC), dimethyl carbonate (DMCO), or the like. diethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), Vinyl carbonate (VC), propylene carbonate (PC), combinations of these, and and / or the like. In a further embodiment, the SEI layer can be a conductive polymer as provided herein. may include.

[0040] In another embodiment, the plurality of carbon particles and elemental lithium metal are and graphite particles. In some embodiments, elemental lithium gold The genus includes a plurality of elemental lithium metal particles. In some embodiments, elemental lithium metal is a method for preparing a graphite particle having a surface roughness of at least some of the graphite particles, the surface roughness being determined by the elemental lithium metal. For example, the mixture may include graphite particles and elemental lithium metal particles. Coating the surfaces of the nanoparticles and / or graphite particles with elemental lithium metal The mixture may be homogeneous or substantially homogeneous. The mixture may be a mixture of bulk elemental lithium metal. For example, the bulk elemental lithium metal can be reduced in size. A small number of elemental lithium metal particles and / or graphite particles of a desired size are then In some embodiments, the coating may be applied to at least some of the surfaces. Graphite particles and bulk elemental lithium metal are blended to produce bulk elemental lithium gold. The size of the metal was reduced to obtain a mixture containing graphite particles and elemental lithium metal. do.

[0041] The present invention provides a method for producing a pre-doped electrode for use in an energy storage device. In some embodiments, a pre-lithiated electrode or method is disclosed. Pre-doped with a desired amount of lithium metal containing one or more compositions described herein. Electrodes with such a structure demonstrate improved energy density performance. It has been found that electrodes containing one or more compositions described herein exhibit excellent thermal conductivity after the first charge / discharge cycle. The present invention can be configured to compensate for irreversible capacity losses exhibited by the energy storage device. For example, it is added to porous carbon particles and / or mixed with graphite particles. A quantity of elemental lithium metal may be prelithiated or predoped to a desired degree, e.g. For example, irreversible capacity loss can be compensated to a desired extent.

[0042] Also provided is an energy storage device in which both the anode and cathode are pre-doped. In such an embodiment, the anode and cathode are doped with metal iridium without a separate pre-doping step. For example, electrodes containing elemental metals as described herein may be pre-doped on In the case of an energy storage device including a first electrode including a film and a second electrode, the second electrode is It may be pre-doped without a separate pre-doping step. Then, the elemental metal of the first electrode diffuses into the second electrode and becomes a pre-doping ion source for the second electrode. In some embodiments, the method of manufacturing a pre-doped energy storage device includes independently The pre-doping step may not be included.

[0043] Although this specification has been described primarily with respect to lithium metal, the devices and and / or the treatment method comprises a composition comprising carbon and lithium and / or one or more other metals. For example, the devices and / or processes described herein may be applied to obtain A compound containing one or more of lithium, sodium, potassium, magnesium, and aluminum. The present invention may be applied to obtain a composition comprising the above-mentioned lithium metal. The present invention relates to a form containing one or more of these metals in the "elemental" state as defined and used. It is possible.

[0044] In some embodiments, the electrode active material, such as carbon particles, and elemental metal are combined with one or more It can be mixed with other electrode film components to provide an electrode film mixture. The one or more other electrode film components may include a binder and / or one or more other electrode active materials. In some embodiments, the binder may include a binder component (hereinafter referred to as an electrode active component). The binder may include a fibrillizable binder, such as a fibrillizable polymer. In some embodiments, the binder may be polytetrafluoroethylene (PTFE In some embodiments, the binder may be a fibrillizable fluoropolymer such as The materials used are PTFE, perfluoropolyolefin, polypropylene, polyethylene, and their composites. In some embodiments, the electrochemically active material may comprise an electrochemically active material, a polymer, and / or a polymer mixture thereof. The composite film consists of a single binder material such as a fibrillizable fluoropolymer. For example, the electrode film mixture may contain only a single binder material. In some embodiments, the single binder material may be, for example, PTFE. , one or more other electrode active components may be hard carbon, soft carbon, graphene, mesoporous carbon, Silicon, silicon oxide, tin, tin oxide, germanium, antimony, lithium titanate titanium dioxide, mixtures, alloys, composites of the above materials, and / or the like. In certain embodiments, the electrode film mixture may essentially consist of elemental metal particles. In certain embodiments, the electrochemically active material comprises an electrochemically active material, carbon particles, and fibrillizable binder particles. The polar film mixture is composed of elemental metal particles, carbon particles, and fibrillizable binder particles. It consists of:

[0045] FIG. 1 is a schematic diagram of a cross-sectional side view of an example energy storage device 100. In some embodiments, the energy storage device 100 may be an electrochemical device. In the example, the energy storage device 100 contains lithium, sodium, potassium, magnesium, and and / or aluminum-based energy storage devices. In some embodiments, the energy storage device 100 may be a lithium-ion battery. In some embodiments, the energy storage device may be a battery based on The device 100 is a lithium-based capacitor, such as a lithium ion capacitor. Of course, other energy storage devices are within the scope of the present invention, such as a capacitor-battery. The energy storage device 100 may include a hybrid and / or a fuel cell. A first electrode 102, a second electrode 104, and a separator disposed between the first electrode 102 and the second electrode 104. For example, the first electrode 102 and the second electrode 104 may be provided with a separator 106. The electrodes may be provided adjacent to each other on the opposing surfaces of the electrodes.

[0046] The first electrode 102 may comprise a cathode, the second electrode 104 may comprise an anode, and In some embodiments, the first electrode 102 is a lithium ion In some embodiments, the first electrode 102 may include a cathode of a capacitor. The second electrode 104 may comprise the cathode of a lithium ion capacitor. In a further embodiment, the first electrode 102 may comprise a resistor. The second electrode 104 may comprise the cathode of a lithium ion battery. The anode may include a battery.

[0047] The energy storage device 100 is configured to transmit ions between the electrodes 102, 104 of the energy storage device 100. For example, the electrolyte 122 may include an electrolyte that facilitates the dissolution of the first electrode 102. The electrolyte 122, the first electrode 102, the second electrode 104, and the separator 106. The two electrodes 104 and the separator 106 are housed within the housing 120 of the energy storage device. For example, the housing 120 of the energy storage device may include the first electrode 102, the second electrode 104 and separator 106 are inserted, and the energy storage device 100 is filled with electrolyte 122. After the first electrode 102, the second electrode 104, the separator 106, and the and electrolyte 122 may be physically sealed from the exterior of housing 120.

[0048] The separator 106 is arranged to electrically insulate the two electrodes separated by the separator. For example, the separator 106 may be configured such that Two electrodes, for example, a first electrode 102 and a second electrode 104, are electrically insulated from each other. The electrode can be configured to allow ionic transfer between the two electrodes.

[0049] As shown in FIG. 1, the first electrode 102 and the second electrode 104 are respectively formed of a first current collector 108 and a second current collector 109. The first current collector 108 and the second current collector 110 are connected to corresponding electrodes and external circuits. (not shown) can facilitate electrical coupling between the

[0050] The first electrode 102 is a first electrode on a first surface of the first current collector 108 (e.g., the top surface of the first current collector 108). A first electrode film 112 (e.g., a top electrode film) and a second opposing surface of the first current collector 108 A second electrode film 114 (e.g., a bottom electrode film 114 ) on a surface (e.g., the bottom surface of the first current collector 108 ). Similarly, the second electrode 104 may include a first surface (e.g., a first electrode film 116 (e.g., a top electrode film) on the top surface of the second current collector 110; A second electrode film on a second opposing surface of the second current collector 110 (e.g., the lower surface of the second current collector 110). For example, the separator 106 may be provided with a second electrode film 118 of the first electrode 102. 14 and the second current collector 110 so as to be adjacent to the first electrode film 116 of the second electrode 104. The first surface of the electrode film 1 can face the second surface of the first current collector 108. 12, 114, 116 and / or 118 may be of various suitable shapes, sizes and / or thicknesses. For example, the electrode film can have a thickness of about 60 μm to about 150 μm, including about 80 μm to about 150 μm. It may have a thickness of 1,000 μm.

[0051] In some embodiments, the electrode films 112, 114, 116 and and / or the electrode film such as 118 may include a plurality of carbon particles and a composite as shown herein. A number of elemental lithium metal particles may be included, such as elemental lithium metal, in the electrode film can be pre-doped or pre-lithiated with lithium. In certain embodiments, The plurality of electrode films 112, 114, 116 and 118 are made of elemental metals as described herein. and carbon mixtures, or are produced in a manner that allows them to be included in the processing steps. .

[0052] In some embodiments, an electrode film containing a plurality of carbon particles and elemental lithium metal is provided. Electrodes having a ZnO layer and pre-doped with a desired amount of lithium have improved energy performance. For example, the electrodes may be Precharge the battery to compensate to a desired extent for the irreversible capacity loss that occurs during the initial charge and discharge. In some embodiments, the electrode may be coated with a quantity of lithium-carbon composite. One or more containing particles or a mixture of graphite particles and elemental lithium metal particles The energy storage device may have an electrode film, whereby the energy storage device may be pre-doped. It has been demonstrated that irreversible capacity loss is reduced compared to energy storage devices that do not include electrodes. It is proven.

[0053] As provided herein, in some embodiments, a plurality of carbon particles and elemental lithium The lithium metal particles include a plurality of lithium-carbon composite particles. The lithium-carbon composite particles contain multiple elemental lithium metal particles, such as elemental lithium metal particles, within the pores. The porous carbon particles include

[0054] Exposed areas of elemental lithium metal reduce the potential for undesirable chemical reactions of elemental lithium metal. In order to reduce the amount of lithium metal oxide, the elemental lithium metal as described herein may be covered with a protective SEI layer. the exposed portion of the porous carbon particle is the portion exposed within the pore but below the outer surface of the corresponding porous carbon particle, or The portion that is exposed but is generally aligned with the outer surface of the corresponding porous carbon particle, or the pore cavity The tee and the portion protruding from the outer surface of each porous carbon particle may be used. In some embodiments, the elemental lithium particles can each include two portions. One is within the pores of the carbon particles, e.g., by surface contact or by sealing. The other is the non-exposed portion that is essentially protected by the surface contact, which may be in the pores. The unsealed parts, i.e. exposed parts that are not protected from external chemical reactions, are not covered by the For example, the exposed portion of the elemental lithium metal particles can be covered with a SEI layer. The SEI layer reduces the possibility of undesired chemical reactions with the outside. The lithium-carbon particle mixture or the elemental lithium-carbon composite particle mixture may be used as described herein. It can be produced by exposure to carbonate vapors such as

[0055] 2A-2F show the formation of a porous carbon particle containing elemental lithium metal, such as an elemental lithium metal particle. introduction into the pores and subsequent solid electrolyte interface covering the exposed portions of the elemental lithium metal particles. 2A is a schematic diagram showing the cross-section of an example of a porous carbon particle 200. As shown in FIG. 2A, the porous carbon particle has a plurality of hollow channels extending therethrough. 2B shows a higher magnification of the porous carbon grain. 2 is a schematic cross-sectional view of a porous carbon particle 200 showing several hollow channels or FIG. 2C shows a cross-sectional view of a hollow channel or pore 202 within a porous carbon particle 200. FIG. 2D is a schematic diagram showing an opening 204 on the exterior surface of a porous carbon particle 200 corresponding to elemental lithium. 2 is a schematic cross-sectional view of a hollow channel or pore 202 within a porous carbon particle 200 containing aluminum metal 206. For example, elemental lithium metal 206 can include elemental lithium metal particles. For example, the hollow channels or pores 202 are filled or substantially filled with elemental lithium metal 206. FIG. 2E shows a hollow cavity extending into particle 200 with elemental lithium metal 206 therein. Shown are openings 204 on the exterior surface of the porous carbon particle 200 that correspond to the channels or pores 202. The exposed lithium metal 20 within the openings 202 on the exterior surface of the porous carbon particle 200 shown in FIG. 2D. 2 is a schematic diagram showing the SEI layer 208 on semiconductor substrate 6.

[0056] In some embodiments, the elemental lithium, such as the portion of elemental lithium in contact with the pore surface, Some fraction of the lithium metal is ionized by one or more moieties on one or more of the pore surfaces. For example, some portion of the elemental lithium may be present on one or more of the pore surfaces of the carbon particles. It reacts with the above components and is oxidized, participating in electron transfer reactions, while the element lithium metal The remainder can remain in an oxidation state of zero.

[0057] As discussed herein, porous carbon particles, such as those described with reference to FIG. Cumulative particle size D of about 1 μm to about 20 μm, including about 1 μm to about 15 μm or about 1 μm to about 10 μm 50 Possess In some embodiments, the porous carbon particles can have pores with diameters of about 2 nm to about 2 μm. In some embodiments, the porous carbon particles can have a particle diameter of about 2. In some embodiments, the porous material may have pores having diameters of about 10% to about 20%. The pores of the carbon particles can occupy about 10% to about 80% of the volume of the carbon particles. In an embodiment, the size of the elemental lithium particles is determined by the amount of elemental lithium metal adsorbed onto the porous carbon particles. The porous carbon particles can be selected based on their pore size so that they can be inserted into the pores of the polymer. Cut.

[0058] As described in more detail herein, in some embodiments, the corresponding porous carbon Exposing the exposed portions of elemental lithium metal within the openings in the outer surface of the particle to carbonate vapor The vapor can react with the exposed lithium metal to form the exposed elemental lithium. A protective SEI layer can be formed over the metal parts. For example, the SEI layer can be formed on the porous carbon particles. Cover any exposed elemental lithium metal areas near or at the openings of pores on the exterior surface. The SEI layer may be formed by the reaction of lithium metal with carbonate vapor. In some embodiments, for example, up to about 50%, about 40%, or about 30% of the porous carbon particles Only a portion of the outer surface of the substrate is covered by the SEI layer. In some embodiments, the SEI layer is formed only on exposed or substantially exposed lithium metal On the other hand, the carbon part of the outer surface of the lithium-carbon composite particle does not contain the SEI layer. In some embodiments, the SEI layer is substantially free of lithium metal. It reduces or prevents further reactions with the local environment while allowing the transfer of electrons and ions through it. and allows for the transport of lithium metal when the lithium-carbon particles are used as part of the electrode. The SEI layer can then be used to facilitate the utilization of the electrochemical energy of the lithium. The uranium-carbon composite particles can maintain their original state even during handling. Thus, the lithium-carbon composite particles reduce the possibility of undesirable reactions of elemental lithium. While maintaining the high yield, elemental lithium metal can be used as a raw material in wet or dry processes. Make it possible.

[0059] In another embodiment, the plurality of carbon particles and elemental lithium metal particles are and mixtures containing elemental lithium metal particles. Thus, a mixture containing graphite particles and elemental lithium metal particles may be prepared by mixing the graphite particles with the elemental lithium metal particles. The particles are mixed with bulk elemental lithium metal to reduce the particle size of the bulk elemental lithium metal. In particular, a mixture containing graphite particles and elemental lithium metal particles of a desired size. In some embodiments, the graphite particles and the lithium gold The particles form a homogeneous or substantially homogeneous mixture.

[0060] Graphite particles and bulk elemental lithium metal are described in terms of lithium carbon composite particles. The graphite particles and ballast can be mixed under the same processing conditions as described above. The elemental lithium metal is mixed with a binder in a dry process and compressed without the use of solvents or other liquids. In such an embodiment, such a film can be compressed to form a free-standing film. Avoids any reactivity or explosion hazards inherent when ingredients are used in wet processing film formation. can be avoided.

[0061] As discussed herein, bulk elemental lithium metal is approximately 1 mm 3 Having a volume greater than Bulk elemental lithium metal can be reduced in size to form elemental lithium metal particles. In some embodiments, the elemental lithium metal particles can be between about 0.5 μm and about 10 μm. Cumulative particle diameter D of m 50 In some embodiments, the elemental lithium metal particles may have The cumulative particle diameter D is about 1 μm to about 10 μm or about 1 μm to about 5 μm. 50 For example, For example, one or more pieces of bulk elemental lithium metal may be one or more of the metal pieces described herein. The above process reduces the thickness by approximately 1 mm. 3 The size is reduced from the volume to a cumulative size of about 0.5 μm to about 10 μm. Particle size D 50 In some embodiments, the lithium particles may be a plurality of elemental lithium particles having The mixture containing graphite particles and elemental lithium metal particles has a size ranging from about 1 μm to about 20 μm. Cumulative particle diameter D of m 50 and a cumulative particle diameter D of about 0.5 μm to about 10 μm. 50 of The lithium ion exchange resin contains elemental lithium metal particles.

[0062] (method) FIG. 3 illustrates a method for preparing a mixture containing a plurality of carbon particles and elemental lithium metal. An example process 300 is shown. In some embodiments, a plurality of lithium-carbon composite particles are The process of forming the children includes process 300. In some embodiments, multiple graphs A process for forming a mixture containing feldtite particles and a plurality of elemental lithium metal particles. The process includes a process step 300. As shown in FIG. 3, block 302, carbon particles can be provided. For example, carbon particles can be used as porous carbon particles for preparing lithium-carbon composite particles; or graphite granules for preparing a mixture containing graphite and lithium metal. It can contain children.

[0063] In block 304, elemental lithium metal is provided. Lithium particles are provided to form the lithium-carbon composite particles. To prepare a mixture containing graphite and lithium metal, bulk elemental lithium gold was added. At block 306, the carbon particles and elemental lithium metal are combined to provide A mixture can be provided that contains a plurality of carbon particles and elemental lithium metal. The mixture may include a dry particle mixture. For example, elemental lithium metal particles may be mixed with a porous carbon. Elemental lithium metal particles are inserted into the pores of the elementary particles to form lithium-carbon composite particles. For example, bulk elemental lithium metal and graphite can be mixed with porous carbon particles. Graphite particles can be mixed in to reduce the size of the bulk elemental lithium metal In some embodiments, bulk elemental lithium metal can be reduced to provide lithium ions of desired size. and a mixture containing lithium metal particles and graphite particles. In some embodiments, at least a portion of the bulk elemental lithium metal can be The bulk elemental lithium metal can be melted while reducing its size, and the molten The lithium metal forms a coating on at least a portion of some of the graphite particles. It is possible.

[0064] The process 300 may include a process for forming lithium-carbon composite particles and / or a process for forming lithium-carbon composite particles. The process described herein involves forming a mixture of silicon metal and graphite particles. Additionally, the reaction may be carried out under temperature, pressure, and / or inert conditions. In the present invention, at least a portion of the process 300 involves the use of a carbonate liquid or vapor. In some embodiments, at least a portion of the process 300 is performed in an atmosphere containing carbonate vapor. under air and / or exposure to carbonate liquids of carbon and elemental lithium metal For example, porous carbon particles and elemental lithium metal can be combined. For example, by exposing porous carbon particles and elemental lithium metal to carbonate vapor For example, the porous carbon particles may be used in an atmosphere containing carbonate vapor. and elemental lithium metal. In some embodiments, the method may include exposing the molten metal to a carbonate liquid. Exposing the elemental lithium metal to carbonate vapor and / or carbonate liquid This helps reduce the surface tension of the molten elemental lithium metal, e.g. The elemental lithium metal is then immersed in the porous carbon particles, which increases the wettability of the molten elemental lithium metal. Lead to the hole.

[0065] FIG. 4 illustrates an example process 400 for producing a plurality of lithium-carbon composite particles. At block 402, a plurality of porous carbon particles can be provided. As described above, in some embodiments, the porous carbon particles are conductive carbon particles. In some embodiments, the plurality of porous carbon particles comprises one or more activated carbon particles and / or In some embodiments, the carbon particles may include a plurality of hierarchically structured carbon particles. The porous carbon particles include structured carbon nanotubes, structured carbon nanowires and / or In some embodiments, the porous carbon nanosheets may include a plurality of porous carbon nanosheets. The porous carbon particles may include graphene sheets. In some embodiments, a plurality of The porous carbon particles are mesoporous. In some embodiments, the plurality of porous carbon particles consists of or consists essentially of activated carbon particles. In the present invention, the plurality of porous carbon particles are made of mesoporous particles or are essentially mesoporous. In some embodiments, the plurality of porous carbon particles is hierarchically structured. The carbon nanotubes may be made up of carbon particles that are arranged in a hierarchical structure or may be made up of carbon particles that are essentially hierarchically structured. In some embodiments, the porous carbon particles are surface-treated carbon particles or any of the other surface-treated carbon particles described herein. The carbon particles may be any other type of carbon particle as described above.

[0066] At block 404, a plurality of porous carbon particles is mixed with a plurality of elemental lithium metal particles. In this case, a plurality of lithium-carbon composite particles can be obtained. Elemental lithium metal resides in the pores of the lithium-carbon composite particles. At least some of the pores within the plurality of porous carbon particles contain elemental lithium metal. In some embodiments, at least some of the pores are filled with elemental lithium metal. In some embodiments, all of the pores are filled with elemental lithium metal. or substantially all filled with elemental lithium metal In some embodiments, elemental lithium gold is loaded within the pores of the porous carbon particles. The genus includes elemental lithium metal particles.

[0067] In some embodiments, the porous carbon particles and elemental lithium metal particles are mixed in a mixing apparatus. Mixing in a mixing chamber to insert elemental lithium metal into the pores of the porous carbon particles In some embodiments, elemental lithium metal particles are inserted into the pores. In some embodiments, the elemental lithium metal particles are at least partially melted during the mixing process. and the molten elemental lithium metal is drawn into the mixture, for example, by capillary action and / or by the mixed The low pressure or vacuum inside the cylinder allows the molten element to enter the pores. The lithium metal can be solidified once inside the pores after the porous carbon particles are cooled. In an embodiment, the pores are filled with elemental lithium metal particles and / or resolidified elemental lithium For example, the pores may contain elemental lithium metal particles and / or recrystallized lithium metal particles. The lithium ion exchange layer may be filled or substantially filled with elemental lithium metal.

[0068] In some embodiments, a plurality of porous carbon particles and a plurality of elemental lithium metal particles are The step of combining may include the use of a carbonate liquid or vapor. For example, Either liquid or carbonate vapor can be fed into the mixing device. In some embodiments, The step of combining the plurality of porous carbon particles and the plurality of elemental lithium metal particles is The reaction can be carried out in an atmosphere containing carbon dioxide vapor, or in an atmosphere containing carbon and elemental lithium metal. As described herein, the method includes exposing the carbonyl chloride to a carbonate liquid. Exposure to carbonate vapor or liquid carbonate reduces the surface tension of molten elemental lithium metal. , thereby enhancing the wettability of molten elemental lithium metal and In some embodiments, the carbon dioxide gas is vaporized by using a carbonate vapor or a fluorine vapor. The carbonate liquids are ethylene carbonate (EC), dimethyl carbonate (DMC), Diethyl carbonate (DEC), ethyl methyl carbonate (EMC), vinyl carbonate (VC), propylene carbonate (PC), and / or equivalents. may also contain one.

[0069] In some embodiments, a desired mixture of elemental lithium particles and porous carbon particles is provided. The devices configured to mix the mixture include ribbon mixers, rotary mixers, planetary mixers, etc. Sieves, high shear blenders, ball mills, hammer mills, jet mills, resonant acoustic mixers These include mixers, microwave mixers, and / or air flow mixers.

[0070] In some embodiments, the size of the elemental lithium metal particles is determined by the pore size of the porous carbon material. For example, the particle size of the elemental lithium metal particles can be selected based on: The amount of lithium metal particles is selected to facilitate insertion into the pores of the porous carbon particles. In some embodiments, the pores of the porous carbon particles can be filled with lithium metal particles. Exemplary porous carbon particles can have pores with an average diameter of 100 to 200 mm. is about 1 / 50 to 1 / 10 of the average carbon particle diameter, and about 10% to 80% of the volume of the carbon particles is branched. The corresponding element lithium metal Particles can be selected with a maximum outer diameter small enough to fit into the pores of the carbon particles. In some embodiments, the elemental lithium metal particles are present in the pores of the plurality of porous carbon particles. It is selected to have an average diameter less than the average diameter.

[0071] In some embodiments, the porous carbon particles and elemental lithium metal particles are heated to above atmospheric pressure. They can be mixed together under low pressure. For example, porous carbon particles and elemental lithium gold The metal particles are fed into the internal volume of the mixing chamber of the device and are approximately 1×10 -8 Pa ~ approx. 1×10 5 Pressure in Pa In some embodiments, the porous carbon particles and elemental lithium may be mixed under The metal particles can be mixed at a temperature above room temperature, for example, above about 20° C. In some embodiments, the temperature may be from 20°C to 200°C, including from 50°C to 180°C. In some embodiments, the porous carbon particles and elemental lithium metal particles are heated to a subatmospheric pressure. By mixing under pressure and at temperatures above room temperature, the lithium metal particles are mixed into a porous carbon. This facilitates insertion into the particles.

[0072] In some embodiments, a gas, such as an inert gas, is introduced into the carbon particles and the lithium metal particles. The inert gas may be a noble gas such as argon. In some embodiments, an inert gas may be flowed into the mixing chamber to Facilitates the insertion of lithium metal into the pores of the porous carbon particles. In some embodiments, An inert gas may be flowed during at least a portion of the mixing step. In the embodiment, the inert gas is passed through the porous carbon particles and the lithium metal particles. In some embodiments, the inert gas may be added to the mixing step after the mixing step has started. for example, for about the last 40%, about 30%, about 20%, about 10% or about 5% of the mixing process. In some embodiments, the inert gas flows into the reaction chamber only during the mixing step. The inert gas may be flowed for the entire time, or substantially the entire time, that the inert gas is being The time for which the gas is allowed to flow is determined so that the lithium metal particles are inserted into the pores of the porous carbon particles to a desired extent. You can choose to do so.

[0073] At block 406, a lithium metal layer is formed on the exposed portion of the lithium-carbon composite particles. A solid electrolyte interface (SEI) layer can be formed on the corresponding porous The SEI can be formed on the exposed portions of elemental lithium metal beneath the outer surface of the carbon particles. The layer protects against external environmental factors such as oxygen and / or water that can degrade lithium metal. While limiting or preventing the exposure of that portion of the lithium metal to the components, In some embodiments, the SE The formation of the I layer is achieved by attaching the lithium-carbon composite particles to one or more vaporized charge carriers of the energy storage device. In some embodiments, the vapor contains a solvent. In some embodiments, the carbonate vapor is ethylene carbonate. Carbonate (EC), Dimethyl Carbonate (DMC), Diethyl Carbonate (DEC), Ethyl Carbonate (EC) ethyl methyl carbonate (EMC), vinyl carbonate (VC), propylene carbonate (P C), combinations thereof, and / or the like.

[0074] In some embodiments, a conductive polymer coating is applied over the exposed portion of the lithium metal. In some embodiments, a low vapor deposition (LD) coating may be applied to the surface of the substrate. Polymerization of the monomer at atmospheric pressure produces a conductive polymer coating on the exposed lithium metal. For example, poly(pyrrole) can be formed using pyrrole as a precursor monomer. A polymer coating can be produced that includes pyrrole. In some embodiments, , Polymer coatings include polythiophene, polyfuran, polyaniline, polyacetylene or combinations thereof and / or the equivalent thereof. do.

[0075] In some embodiments, after a desired amount of lithium metal is intercalated into the porous carbon particles, The lithium-carbon composite particles can be exposed to carbonate vapor. In this embodiment, the lithium-carbon composite particles are mixed with carbonate vapor in the mixing chamber, e.g. The carbonate-containing solvent may be exposed to the interior volume of the chamber, the vapor of which may be mixed with the lithium metal. After mixing, the mixture is evaporated to form the SEI layer in the mixing chamber so that it can react with the exposed portions of the In some embodiments, the lithium-carbon particles can be provided in different The particles can then be transported to a chamber where they are exposed to carbonate vapor. Exposure of lithium-carbon composite particles to carbonate vapor has been shown to The carbonate is in the gas phase or substantially in the gas phase so that it can react with the lithium metal. This can be done under a variety of temperature and pressure conditions. In an embodiment, the pressure in the interior volume is determined by the temperature of the interior volume, and the pressure in the interior volume is determined by the temperature of the interior volume. The vapor pressure of the carbonate mixture can be kept lower than that of the carbonate mixture.

[0076] As described herein, in some embodiments, exposure to carbonate vapor This can be done during the process of combining the plurality of porous carbon particles with elemental lithium metal, For example, exposure to carbonate vapor can be used to form an SEI layer. Therefore, it is possible to promote both the insertion of lithium metal into the pores of the carbon particles and the formation of an SEI layer. This can be done.

[0077] In some embodiments, the carbon portion of the outer surface of the lithium-carbon composite does not include an SEI layer. or substantially free of exposed elemental lithium metal, and only or substantially free of exposed elemental lithium metal The carbonate-containing vapor was then introduced so that the SEI layer formed only on the elemental lithium metal. Capable of reacting only or substantially only with elemental lithium metal In some embodiments, the SEI layer can protect the exposed lithium metal, This allows for further processing of the lithium-carbon composite particles and / or To facilitate the production of electrode films and / or electrode film mixtures containing composite particles. In some embodiments, the SEI layer can be used to further reduce the contact between lithium metal and the external environment. To allow both ion and electron transport while reducing or preventing reactions that may occur. The transport of ions and electrons in the SEI layer plays a major role in the operation of energy storage devices. This allows access to the conductive lithium metal within the porous carbon particles, making the porous carbon particles the first Facilitating access to lithium-derived electrical energy without cleaving or cracking In some embodiments, the SEI layer inhibits reaction of the exposed lithium metal with the liquid. This prevents or prevents the use of wet or dry electrode fabrication processes, such as those involving slurry solutions. This facilitates the use of lithium-carbon composite particles in manufacturing processes.

[0078] With reference to Figure 5, prepare a mixture using bulk elemental lithium metal and graphite. A process 500 for producing lithium gold is described below. In block 502, bulk elemental lithium gold is As described herein, bulk elemental lithium metal can be May include sheets and / or chunks of bare lithium metal, or other forms of bulk metal. At block 504, graphite particles can be provided. At block 506, In the present study, bulk elemental lithium metal and graphite particles were mixed together to produce elemental lithium A mixture containing metal and graphite particles can be provided.

[0079] In some embodiments, bulk elemental lithium metal is mixed with graphite particles. The process involves reducing the size of bulk elemental lithium metal. So, the mixing process is to convert the bulk elemental lithium metal into elemental lithium of the desired size. The size of the particles is reduced and the particles are mixed with elemental lithium metal particles and graphite. A homogenous or substantially homogenous mixture containing the cellulose particles can be obtained. In some embodiments, at least a portion of the lithium metal is a bulk elemental lithium metal. During the reduction in size, the lithium metal can be melted and the molten lithium metal can be melted into graphite. A coating may be formed on at least a portion of some of the particles. In some embodiments, the mixture containing graphite particles and elemental lithium metal comprises: Graphite particles, a plurality of elemental lithium metal particles, and / or at least some Coating the surface of graphite particles with elemental lithium. For example, mixtures thereof The material comprises graphite particles, elemental lithium metal particles and / or at least some of the graphite particles. A homogeneous or substantially homogeneous mixture containing elemental lithium metal on one or more surfaces of the phytoparticle. It may also comprise a mixture.

[0080] In some embodiments, bulk elemental lithium metal is mixed with graphite particles. The process involves blending bulk elemental lithium metal with graphite particles. In some embodiments, a Waring® blender can be used. In some embodiments, the blend of bulk elemental lithium metal and graphite particles is The conditions are adjusted to obtain a homogeneous or substantially homogeneous mixture of aluminum metal particle size. In some embodiments, the conditions of the mixing process can be selected based on the duration of the mixing process. the duration, the magnitude of shear force, the temperature of the mixing process, the tip of the mixing blades and / or paddles speed, type of mixer, environment inside the mixing chamber, order in which materials are fed into the mixing chamber; and / or by the amount of material introduced into the mixing chamber.

[0081] In some embodiments, materials other than graphite or materials other than graphite The material, which is made by adding lithium to graphite, can be mixed with bulk elemental lithium metal. For example, one or more other electrode film materials can be mixed with bulk elemental lithium metal. to obtain a homogenous or substantially homogenous mixture containing elemental lithium metal particles of a desired size. In some embodiments, the one or more other materials can be silicon, oxide, or the like. Silicon, tin, tin oxide, carbon composites containing carbon, silicon and tin, and combinations thereof and / or the like.

[0082] In some embodiments, a mixture containing graphite particles and lithium metal particles. can be directly used to form dry particle electrode films in dry manufacturing processes. In some embodiments, the graphite particles and elemental lithium metal are then mixed. The mixture containing the lithium metal particles can be treated to form an SEI layer around the lithium metal particles. , thereby reducing or preventing further reaction of, for example, lithium metal with the external environment. In some embodiments, one or more of the methods for forming the SEI layer described with reference to FIG. The above treatments can be applied. For example, the mixture can be heated with, for example, carbonate vapor. In some embodiments, the electrolyte may be exposed to a vaporized electrolyte solvent such as carbonate vapor. The gas may comprise one or more of the compositions described herein. In some embodiments, The above process allows for wet processing, such as wet slurry processing, to form an electrode film. This can facilitate the use of lithium metal in treatment processes.

[0083] FIG. 6 illustrates an energy storage device electrode film containing carbon particles and elemental lithium metal. An example of a dry process 600 for manufacturing an electrode film is shown. It may contain lithium-carbon composite particles or a mixture of graphite particles and elemental lithium metal. In some embodiments, the electrode can be an energy storage device as described with reference to FIG. The electrode of the device 100 may be a lithium ion In some embodiments, the electrode comprises an anode of a lithium ion capacitor. The anode includes:

[0084] At block 602, carbon particles and elemental lithium metal can be provided. In some embodiments, the step of providing elemental lithium metal and carbon particles comprises providing a plurality of lithium In some embodiments, elemental lithium metal and The step of providing carbon particles comprises providing a mixture containing elemental lithium metal and graphite particles. In some embodiments, the method includes providing a plurality of lithium-carbon composite particles and and / or the mixture containing the elemental lithium particles and the graphite particles may be In some embodiments, the block may be manufactured according to one or more process steps. 602 may include any of the methods described in blocks 302, 304, 402, and / or 502. This includes the process.

[0085] At block 604, the carbon particles and elemental lithium metal are mixed with one or more other electrode fillers. In some embodiments, the electrode film mixture can be mixed with the luminous component to obtain an electrode film mixture. In the present invention, one or more other electrode film components may include a binder and / or one or more other electrodes. In some embodiments, the binder comprises, for example, a fibrillizable polymer. In some embodiments, the binder may include a fibrillizable binder comprising Inda is a fibrillating agent for fibrillating fluoropolymers such as polytetrafluoroethylene (PTFE). In some embodiments, the binder comprises PTFE, perfluoropolyolefin. , polypropylene, polyethylene, copolymers thereof, and / or polymers thereof In some embodiments, the electrode film mixture comprises a blend of The binder may be a single binder such as a fluoropolymer that can be acrylated. For example, the electrode film mixture may contain only a single binder, and the single binder In some embodiments, one or more other electrode active components may be a hard Hard carbon, soft carbon, graphene, mesoporous carbon, silicon, silicon oxide, tin, Tin oxide, germanium, lithium titanate, titanium dioxide, or mixtures of these materials. In some embodiments, the block Block 604 may be any of the blocks 306, 404, 406, and / or 506. In a particular embodiment, block 604 includes the steps of block 406. Thus, in some embodiments, block 604 may include The method includes exposing the lithium-carbon composite particles to a vapor containing a condensed electrolyte solvent. The method includes the step of forming a

[0086] In some embodiments, the combining step of block 604 is a dry process. For example, elemental lithium metal particles and carbon particles can be processed dry, i.e., without the use of solvents or additives. In a process that is free or substantially free of any of the other electrode film components, In some embodiments, the dry particles may be mixed together to provide a dry particle electrode film mixture. a plurality of lithium-carbon composite particles or elemental lithium metal particles and graphite particles; The mixture containing the one or more other components of the electrode of the energy storage device is mixed in a dry mixing process. The dry particle electrode film mixture can be obtained by mixing the In some embodiments, block 604 includes fibrillating elemental lithium metal particles and carbon particles. The process can include combining the material with a binder that is recyclable.

[0087] At block 606, an electrode film including an electrode film mixture can be obtained. For example, the electrode film may be used in a lithium ion battery or a lithium ion capacitor. In some embodiments, the electrode film mixture may be a film for use as an anode. The composite contains a fibrillizable binder, and the formation of the electrode film is performed by a fibrillation process. The fibrillation process comprises the step of: A matrix, lattice and / or a matrix of fibrils that provides structural support for the other components of the film. For example, the binder material in the electrode film mixture can be fibrillated to form a web. The electrode film mixture is then melted to form a free-standing dry particle electrode film. In some embodiments, shear forces can be applied to the binder, such as in a blending process. For example, a jet mill treatment can be used to form fibrils. It is possible to carry out a crushing process.

[0088] In certain embodiments, the free-standing electrode film is essentially composed of elemental metal particles, carbon particles, and fibrillated binder particles. In certain embodiments, the free-standing electrode film The matrix is ​​composed of elemental metal particles, carbon particles, and fibrillated binder particles. In some embodiments, the elemental metal particles and the carbon particles are composite particles as described herein.

[0089] In some embodiments, a wet processing step for manufacturing an electrode for an energy storage device is provided. In some embodiments, the electrode film can be formed by The wet processing steps for manufacturing the electrodes of the storage device include one or more electrode components that contain the electrode active components. preparing a liquid solution containing the component, and forming an electrode film using the liquid solution. In some embodiments, the liquid solution may be used to bond the electrodes. In the forming process, slot die coating, gravure coating, reverse slot Roll coating, knife over roll coating, metering rod coating The coating may be performed using one or more of the following techniques: spray coating, curtain coating and / or dip coating.

[0090] In some embodiments, the electrode, e.g., a lithium ion battery or a lithium ion The electrodes of the capacitor are fabricated in one or more of steps 300, 400, 500 and / or 600. For example, an electrode may include one or more electrode films attached to a current collector. For example, the electrodes may include a film bonded to opposing surfaces of a current collector. In some embodiments, the dry particle electrode film may include a respective electrode film. Mu may be bonded to the surface of the current collector, for example, directly to the current collector by means such as lamination processing. In some embodiments, the interposed adhesive layer can facilitate the bonding of the electrode film to the current collector. Therefore, a method for manufacturing a pre-doped electrode for use in an energy storage device is provided, which includes one or more of the processing steps 300, 400, 500, and / or 600. For example, the energy storage device can be manufactured by a method that includes a step of providing carbon particles, a step of providing elemental metal, and a step of mixing the carbon particles with elemental lithium metal to obtain a mixture containing the carbon particles and the elemental lithium metal, such as in processing step 300. It can also be manufactured by a method that includes a step of providing a plurality of porous carbon particles, a step of mixing the plurality of porous carbon particles with a plurality of elemental lithium metal particles to obtain a plurality of lithium-carbon composite particles, and a step of forming a solid electrolyte interface layer on the exposed portion of the lithium metal of the lithium-carbon composite particles, such as in processing step 400. It can also be manufactured by a method that includes a step of providing bulk elemental lithium metal, a step of providing graphite particles, and a step of mixing the bulk elemental lithium metal with the graphite particles to obtain a mixture containing the elemental lithium metal and the graphite particles, such as in processing step 500. And / or it can be manufactured by a method that includes a step of providing carbon particles and elemental lithium metal, a step of mixing the carbon particles and the elemental lithium metal with one or more other electrode film components to obtain an electrode film mixture, and a step of forming an electrode film containing the electrode film mixture, such as in processing step 600. For example, the energy storage device can be manufactured by a method that includes a step of providing carbon particles, a step of providing elemental metal, and a step of mixing the carbon particles with elemental lithium metal to obtain a mixture containing the carbon particles and the elemental lithium metal, such as in processing step 300. It can also be manufactured by a method that includes a step of providing a plurality of porous carbon particles, a step of mixing the plurality of porous carbon particles with a plurality of elemental lithium metal particles to obtain a plurality of lithium-carbon composite particles, and a step of forming a solid electrolyte interface layer on the exposed portion of the lithium metal of the lithium-carbon composite particles, such as in processing step 400. It can also be manufactured by a method that includes a step of providing bulk elemental lithium metal, a step of providing graphite particles, and a step of mixing the bulk elemental lithium metal with the graphite particles to obtain a mixture containing the elemental lithium metal and the graphite particles, such as in processing step 500. And / or it can be manufactured by a method that includes a step of providing carbon particles and elemental lithium metal, a step of mixing the carbon particles and the elemental lithium metal with one or more other electrode film components to obtain an electrode film mixture, and a step of forming an electrode film containing the electrode film mixture, such as in processing step 600. For example, the energy storage device can be manufactured by a method that includes a step of providing carbon particles, a step of providing elemental metal, and a step of mixing the carbon particles with elemental lithium metal to obtain a mixture containing the carbon particles and the elemental lithium metal, such as in processing step 300. It can also be manufactured by a method that includes a step of providing a plurality of porous carbon particles, a step of mixing the plurality of porous carbon particles with a plurality of elemental lithium metal particles to obtain a plurality of lithium-carbon composite particles, and a step of forming a solid electrolyte interface layer on the exposed portion of the lithium metal of the lithium-carbon composite particles, such as in processing step 400. It can also be manufactured by a method that includes a step of providing bulk elemental lithium metal, a step of providing graphite particles, and a step of mixing the bulk elemental lithium metal with the graphite particles to obtain a mixture containing the elemental lithium metal and the graphite particles, such as in processing step 500. And / or it can be manufactured by a method that includes a step of providing carbon particles and elemental lithium metal, a step of mixing the carbon particles and the elemental lithium metal with one or more other electrode film components to obtain an electrode film mixture, and a step of forming an electrode film containing the electrode film mixture, such as in processing step 600. For example, the energy storage device can be manufactured by a method that includes a step of providing carbon particles, a step of providing elemental metal, and a step of mixing the carbon particles with elemental lithium metal to obtain a mixture containing the carbon particles and the elemental lithium metal, such as in processing step 300. It can also be manufactured by a method that includes a step of providing a plurality of porous carbon particles, a step of mixing the plurality of porous carbon particles with a plurality of elemental lithium metal particles to obtain a plurality of lithium-carbon composite particles, and a step of forming a solid electrolyte interface layer on the exposed portion of the lithium metal of the lithium-carbon composite particles, such as in processing step 400. It can also be manufactured by a method that includes a step of providing bulk elemental lithium metal, a step of providing graphite particles, and a step of mixing the bulk elemental lithium metal with the graphite particles to obtain a mixture containing the elemental lithium metal and the graphite particles, such as in processing step 500.

[0091] In some embodiments, the energy storage device comprises one or more electrode frames as described herein. For example, electrodes for energy storage devices can be manufactured using the methods described herein. In some embodiments, the electrode film may include one or more of the electrode films described herein. The energy storage device may include an outer housing. The electrodes can be inserted into the housing. One or more other electrodes and / or one or more separators may be inserted therein. The housing is then sealed so that a desired amount of electrolyte is introduced into the energy storage device housing. After being sealed, the container may be sealed.

[0092] FIG. 7 illustrates an apparatus 700 configured to prepare one or more compositions described herein. FIG. 7 is a schematic diagram of an example of a device 700. For example, the device 700 may include an energy The present invention is configured to produce bulk material for use in manufacturing electrodes of gas storage devices. As shown in FIG. 7, carbon particles 702 and elemental lithium gold are The element 704 is a crystalline lithium metal 704 that is formed by subjecting the carbon particles 702 and elemental lithium metal 704 to one or more of the processes described herein. are fed into the internal volume of the mixing chamber 706 of the device 700 so as to be mixed according to the process. The device 700 may be configured to produce a plurality of lithium-ion batteries according to one or more process steps described herein. A mixture containing carbon composite particles or graphite particles and elemental lithium metal is obtained. For example, the device 700 may be configured to perform the processes described with reference to FIGS. 7. The carbon particles 702 and elemental lithium metal 704 are mixed according to a processing process to produce a corresponding porous carbon. Lithium-carbon composite particles having lithium metal in the pores of the particles, or lithium metal (At least some of the surfaces of the elemental lithium metal particles and / or the graphite particles The elemental lithium metal coating formed in the In some embodiments, the apparatus 70 can be configured to provide a mixture having 0 is ribbon mixer, rotary mixer, planetary mixer, high shear blender ball mill, hammer mill, jet mill, resonant acoustic mixer, microwave mill The mixing device may include a mixer, a mixer, and / or an air flow mixer. EXAMPLES

[0093] 8A-8C show a process for preparing a dry particulate mixture from bulk elemental lithium metal according to one embodiment. Photographs showing various steps in the preparation process. Graphite particles and lithium metal silicide in the mixing chamber of the NG Blender In this example, approximately 23.3 g (grams) of graphite powder and bulk elemental lithium Approximately 0.68 g of lithium metal is mixed in a blender. Graphite powder and lithium metal are was blended about 36 times with a pulse interval of about 5 seconds. In FIG. 8C, about 1.7 g of PTFE was The mixture was added to a blend containing graphite powder and lithium metal. The graphite powder and lithium metal were blended about 24 times with a pulse interval of about 5 seconds to obtain PTFE, graphite, graphite powder, and lithium metal. An electrode film mixture containing lite powder and lithium metal was obtained.

[0094] 9A and 9B show an example of a PTFE, graphite powder and lithium metal composite. The electrochemical properties of two coin half-cells containing free-standing electrode films formed using the mixtures were 1 is a graph showing the performance of the half-cell. The half-cell has a lithium metal counter electrode and a polyolefin Paratera and LiPF in a carbonate-based solvent 6 and further comprising an electrolyte containing 9A and 9B show the first delithiation without a prior galvanostatic lithiation step. 9A and 9B show the change in voltage of a coin half-cell after the ammoniating step. The y-axis shows voltage in volts (V) and the x-axis shows lithium ion (Li-ion) in ampere-hours (Ah). These voltage curves show the ionization capacity of the electrodes of the device (e.g., PTFE, A free-standing electrode formed using a mixture containing graphite powder and lithium metal. The amount of electrochemically available lithium metal in the film can be estimated. A 9A coin cell has a capacity of about 2.5 milliamp hours at a cutoff voltage of 1.5V. The coin half-cell shown in FIG. 9B has a capacity of about 3 mAh at the same cutoff voltage. The amount was shown.

[0095] The delithiation performance was determined by the electrochemically available lithium in the graphite composite electrode. The amount of lithium metal can be dependent on the amount of lithium metal in the supply of electrochemical energy. Lithium metal plays several roles. For example, it is involved in the formation of the SEI on the graphite surface. Electrochemical energy for lithium ions in graphite and free lithium metal For example, from FIG. 9A, the graph The presence of free lithium metal in the ZnO electrode film and the presence of intercalated lithium It can be seen that lithium ions are present. The delithiation process, which is nearly zero voltage, up to ampere hours, results in free lithium metal. On the other hand, the voltage rises from about 1 mA to about 2.5 mA. The increase in the temperature can be attributed to the deintercalation process of lithium ions in graphite. In contrast to FIG. 9A, FIG. 9B shows that the voltage is about 0.1 volts at the beginning of the delithiation process. Therefore, the delithiation process involves the desorption of lithium ions into graphite. These two examples support the possibility that tercalation is occurring almost exclusively. The robustness of the dry electrode processing steps to accommodate bulk lithium metal; The capacity from the bulk lithium metal in the final electrode can be adjusted to a desired value, for example, by the input amount. Demonstrates easily adjustable performance.

[0096] 7 and 8A-8C, or the carbon material is mixed with the bulk elemental lithium material. For example, see Figures 3-6 herein, using other devices suitable for mixing with Methods other than those described may be implemented to produce bulk electrode materials, films, and / or energy It will be appreciated that a ghee storage device can be formed.

[0097] Headings used herein are for reference and to identify the various sections. These headings are used to locate the concepts described. These concepts may have applicability throughout the entire specification.

[0098] The disclosed embodiments are provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art. The general principles defined herein may be modified without departing from the spirit or scope of the present invention. The present invention is not limited to the embodiments shown in this specification. The present invention is not limited to the above, but is intended to cover the broadest possible range consistent with the principles and novel features disclosed herein. It should be accepted within limits.

[0099] In the above description, novel features of the present invention as applied to various embodiments have been pointed out. Those skilled in the art will recognize that various omissions, substitutions, and modifications in the form and details of the devices or methods described may be made without departing from the spirit and scope of the present invention. It will be understood that modifications and variations are possible without departing from the scope of the invention.

Claims

1. A first electrode, a second electrode, and a separator between the first electrode and the second electrode. 、 At least one of the first electrode and the second electrode comprises carbon particles and an elemental metal. Energy storage device.

2. The carbon particles include porous carbon particles, each of which has a plurality of pores, At least some of the pores of the porous material receive at least some of the elemental metal.

10. The energy storage device of claim 1.

3. The porous carbon particles include activated carbon.

3. The energy storage device of claim 2.

4. The porous carbon particles include hierarchically structured carbon.

3. The energy storage device of claim 2.

5. The porous carbon particles include mesoporous carbon.

3. The energy storage device of claim 2.

6. and further comprising a solid electrolyte interface (SEI) layer covering the exposed portion of the elemental metal. The energy storage device of claim 2 .

7. The SEI layer covers the exposed portions of the elemental metal underlying the outer surface of the corresponding porous carbon particle.

6. The energy storage device of claim 5.

8. At least one of the first electrode and the second electrode contains elemental metal and carbon particles. Contains dry electrode film 6. The energy storage device of claim 5.

9. The carbon particles include graphite particles.

10. The energy storage device of claim 1.

10. At least one of the first electrode and the second electrode includes an anode.

10. The energy storage device of claim 1.

11. The anode is an anode of a lithium ion battery or a lithium ion capacitor. is 11. The energy storage device of claim 10.

12. The elemental metal comprises elemental lithium metal particles.

10. The energy storage device of claim 1.

13. 1. A method of manufacturing an energy storage device, comprising: A process for combining elemental lithium metal with a plurality of carbon particles to form an electrode film composite. With forming an electrode film from the electrode film mixture; The method includes:

14. Forming a first electrode and a second electrode, at least one of which includes the electrode film and a current collector. And a process of inserting a separator between the first electrode and the second electrode; Further equipped The method of claim 13.

15. The plurality of carbon particles includes a plurality of porous carbon particles, each of the porous carbon particles having a plurality of fine particles. Has holes The method of claim 14.

16. The plurality of porous carbon particles comprises at least one of activated carbon and hierarchically structured carbon. One containing The method of claim 15.

17. The step of combining the elemental lithium metal and the plurality of carbon particles comprises: At least some of the pores receive at least some of the plurality of elemental lithium metals. mixing said elemental lithium metal and said plurality of porous carbon particles so as to form a Includes The method of claim 15.

18. forming a solid electrolyte interface (SEI) layer on the exposed portions of said elemental lithium metal. Further equipped 20. The method of claim 17.

19. The step of forming an SEI layer may include forming a layer of the elemental lithium beneath the outer surface of the corresponding porous carbon particle. The process of covering exposed metal parts Includes 20. The method of claim 18.

20. The step of forming the SEI layer includes exposing the exposed portion of the elemental lithium metal to an electrolyte solvent vapor. Process Includes 20. The method of claim 18.

21. The step of exposing the exposed portion of elemental lithium to the electrolyte solvent vapor exposing said exposed portion of said mold to carbonate vapor. Includes 21. The method of claim 20.

22. The carbon particles include graphite particles. The method of claim 13.

23. The electrode film mixture is a substantially homogenous mixture.

23. The method of claim 22.

24. the elemental lithium metal comprising elemental lithium metal particles; Producing bulk elemental lithium metal; Reducing the size of the bulk elemental lithium metal to form a plurality of elemental lithium metal particles. The process of Further equipped The method of claim 13.

25. The step of combining the elemental lithium metal with the plurality of carbon particles may include and mixing the dry metal with a plurality of dry carbon particles to form a dry electrode film mixture. include The method of claim 13.

26. At least one of the first electrode and the second electrode is a lithium ion battery or Including the anode of a lithium ion capacitor The method of claim 14.

27. disposing the first electrode, the separator and the second electrode within a housing. Including The method of claim 14.

28. Adding an electrolyte to the housing and connecting the electrolyte to the first electrode and the second electrode. The method further comprises the step of contacting the 28. The method of claim 27.

29. The step of contacting the first electrode and the second electrode includes pre-doping the second electrode. The process includes the step of:

30. The method of claim 28.

30. A mixture of bulk materials for producing a lithium ion energy storage device, comprising: Elemental lithium metal; Activated carbon particles and A mixture containing:

31. 31. A mixing device having an interior volume containing the mixture of claim 30.

32. The internal volume contains an inert gas.

32. The mixing device of claim 31.

33. The activated carbon particles include graphite.

32. The mixing device of claim 31.

34. The activated carbon particles include porous carbon particles having the elemental lithium metal within the pores.

32. The mixing device of claim 31.

35. The internal volume further comprises a vapor of an electrolyte solvent.

35. The mixing device of claim 34.

36. A pre-doped composition for use in an energy storage device comprising the mixture according to claim 30. electrode.

37. combining elemental lithium metal with a plurality of carbon particles to form an electrode film composite. and, forming a first electrode film from the electrode film mixture; 23. An energy storage device manufactured by a process comprising:

38. Energy produced by a process comprising the method according to any one of claims 13 to 29. -Storage device.

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