EP4107800A1 - Fast charging pre-lithiated silicon anode - Google Patents
Fast charging pre-lithiated silicon anodeInfo
- Publication number
- EP4107800A1 EP4107800A1 EP21711137.6A EP21711137A EP4107800A1 EP 4107800 A1 EP4107800 A1 EP 4107800A1 EP 21711137 A EP21711137 A EP 21711137A EP 4107800 A1 EP4107800 A1 EP 4107800A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- lithium
- anode
- battery
- metal powder
- printable
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052710 silicon Inorganic materials 0.000 title claims description 35
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims description 31
- 239000010703 silicon Substances 0.000 title claims description 31
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 300
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 234
- 238000009792 diffusion process Methods 0.000 claims abstract description 39
- 239000006183 anode active material Substances 0.000 claims abstract description 14
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- 239000002491 polymer binding agent Substances 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 32
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 31
- 239000006254 rheological additive Substances 0.000 claims description 29
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- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
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- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 4
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
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- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the present invention relates to a battery with a cathode and a porous anode having improved lithium diffusion kinetics and surface conductivity.
- Lithium and lithium-ion secondary or rechargeable batteries have found use in certain applications such as in cellular phones, camcorders, and laptop computers, and even more recently, in larger power application such as in electric vehicles and hybrid electric vehicles. It is preferred in these applications that the secondary batteries have the highest specific capacity possible but still provide safe operating conditions and good cyclability so that the high specific capacity is maintained in subsequent recharging and discharging cycles.
- each construction includes a positive electrode (or cathode), a negative electrode (or anode), a separator that separates the cathode and anode, an electrolyte in electrochemical communication with the cathode and anode.
- a positive electrode or cathode
- a negative electrode or anode
- a separator that separates the cathode and anode
- an electrolyte in electrochemical communication with the cathode and anode.
- lithium ions are transferred from the anode to the cathode through the electrolyte when the secondary battery is being discharged, i.e., used for its specific application.
- electrons are collected from the anode and pass to the cathode through an external circuit.
- the lithium ions are transferred from the cathode to the anode through the electrolyte.
- New lithium-ion cells or batteries are initially in a discharged state.
- lithium moves from the cathode material to the anode active material.
- the lithium moving from the cathode to the anode reacts with an electrolyte material at the surface of the graphite anode, causing the formation of a passivation film on the anode.
- the passivation film formed on the graphite anode is also called solid electrolyte interface (SEI).
- SEI solid electrolyte interface
- the lithium consumed by the formation of the SEI is not returned to the cathode. This results in a lithium-ion cell having a smaller capacity compared to the initial charge capacity because some of the lithium has been consumed by the formation of the SEI.
- the partial consumption of the available lithium on the first cycle reduces the capacity of the lithium-ion cell. This phenomenon is called irreversible capacity and is known to consume about 10% to more than 20% of the capacity of a lithium ion cell. Thus, after the initial charge of a lithium-ion cell, the lithium-ion cell loses about 10% to more than 20% of its capacity.
- lithium powder can be stabilized by passivating the metal powder surface with carbon dioxide such as described in U.S. Pat. Nos. 5,567,474, 5,776,369, and 5,976,403, the disclosures of which are incorporated herein in their entireties by reference.
- the CO2 passivated lithium metal powder can be used only in air with low moisture levels for a limited period of time before the lithium metal content decays because of the reaction of the lithium metal and air.
- Another solution is to apply a coating such as fluorine, wax, phosphorus or a polymer to the lithium metal powder such as described in U.S. Patent Nos. 7,588,623,
- Silicon and silicon-containing anodes have been developed for decades because of their high theoretical charge capacity (4200 mA h/g).
- current silicon anodes may be hampered with various issues, for example high irreversible capacity and short cycle life due to issues with volume expansion.
- the silicon particles alloy with lithium the particle volume may expand up to 400%.
- the present invention provides a battery having a cathode and a porous anode lithiated with a lithium powder, lithium particulates or a printable lithium formulation.
- the pores are formed, for example, by lithium diffusing from the printable lithium composition into an anode active material.
- a battery with a porous anode as described herein will have improved lithium diffusion kinetics and or gradient porosity leading to increased fast charging capability and improved low temperature performance.
- the anode active material is a silicon containing active material.
- the silicon active material is alloyed with lithium particles to form a three-dimensional porous framework in the anode having an increased electrode porosity and reduced electrode deterioration from volume expansion due to the buffering effect of the pores.
- a highly conductive porous layer may also be formed on a surface of the anode.
- the porous conductive surface layer and gradient porosity enables high rates of charging by effectively lowering the areal current density and by having increased conductivity and allowing for faster diffusion of lithium at the electrode surface and in the electrode bulk, thereby allowing thicker electrodes while decreasing the likelihood of lithium plating on the anode surface.
- the anode active material is selected from the group consisting a single or a combination including graphite, hard carbon, graphite-SiOx composite, SiOx, SiO, S1O2, Si powder, Si film, SiC, Si/C composite, Si-based alloys, graphite-SnO, Sn/C composite, and other lithium ion battery and lithium ion capacitor anode materials.
- the printable lithium formulation may be comprised of a lithium metal powder, a polymer binder compatible with the lithium metal powder, a rheology modifier compatible with the lithium metal powder, and a solvent compatible with the lithium metal powder and with the polymer material.
- the polymer material may form a polymer film on the surface of the electrode that acts as a lithiation control layer.
- the lithiation control layer may regulate lithium diffusion and slow the rate of dry state pre-lithiation that can occur during lamination of the lithium to the surface of the negative electrode and may subsequently allow for the dissipation of heat generation during storage of the electrode materials.
- the formed layer can also function as an artificial solid electrolyte interphase.
- the polymer can create a flexible, electronically insulating layer that can expand and contract with the silicon anode, maintaining integrity while allowing lithium ions to transfer across the layer.
- the printable lithium By depositing the printable lithium as a thin stripe in the Y-plane as an alternating pattern between silicon anode stripes, the silicon anode material can expand in the X-plane alleviating electrochemical grinding and loss of particle electrical contact.
- the printing method can provide a buffer for expansion.
- the printable lithium formulation is used to form the anode, it could be co-extruded in a layered fashion along with the cathode and separator, resulting in a solid-state battery.
- FIG. 1A is a SEM backscatter image of a graphite electrode containing 10% SiO treated using a printable lithium composition.
- FIG. 1B is a SEM backscatter image of the graphite electrode containing 10% SiO after completion of the lithium diffusion.
- FIGS. 2A-C are plots comparing gas generation for baseline cells versus cells treated with a printable lithium composition under different conditions.
- FIG. 3A is a reflected light microscopy image of a SiO electrode surface with SLMP initially deposited at its surface.
- FIG. 3B is a reflected light microscopy image of a SiO electrode surface five minutes after SLMP is deposited at its surface.
- FIG. 3C is a reflected light microscopy image of a SiO electrode surface fifteen minutes after SLMP is deposited at its surface.
- FIG.3D is a reflected light microscopy image of a SiO electrode surface twenty minutes after SLMP is deposited at its surface.
- FIG. 3E is a reflected light microscopy image of a SiO electrode surface with a printable lithium composition initially deposited at its surface.
- FIG. 3F is a reflected light microscopy image of a SiO electrode five hours surface after printable lithium composition is deposited at its surface.
- FIG. 3G is a reflected light microscopy image of a SiO electrode surface fifteen hours after printable lithium composition is deposited at its surface.
- FIG. 3H is a reflected light microscopy image of a SiO electrode surface twenty hours after printable lithium composition is deposited at its surface.
- FIG. 4 is a plot comparing differential capacity (dQ/d ⁇ /) versus potential ( V) during first charge between baseline and cells treated with a printable lithium composition.
- FIG. 5A is a plot showing AC impedance for baseline cells and cells treated with a printable lithium composition as measured after formation cycle.
- FIG. 5B is a plot showing AC impedance for baseline cells and cells treated with a printable lithium composition after cycling at the end of cycle life (20% capacity loss).
- the terms “comprise,” “comprises,” “comprising,” “include,” “includes” and “including” specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.
- the term “consists essentially of” (and grammatical variants thereof), as applied to the compositions and methods of the present invention means that the compositions/methods may contain additional components so long as the additional components do not materially alter the composition/method.
- the term “materially alter,” as applied to a composition/method refers to an increase or decrease in the effectiveness of the composition/method of at least about 20% or more.
- a battery comprising a cathode and a porous silicon anode lithiated with a lithium source.
- the anode is comprised of a silicon active material with carbon nanotubes.
- suitable lithium sources may include lithium powder, lithium particulates, lithium mesh or a printable lithium composition.
- the printable lithium composition comprises a lithium metal powder, a polymer binder, a rheology modifier and may further include a solvent.
- the polymer binder may be compatible with the lithium metal powder.
- the rheology modifier may be compatible with the lithium metal powder and the polymer binder.
- the solvent may be compatible with the lithium metal powder and with the polymer binder.
- the silicon active material is lithiated with a lithium powder, lithium particulates or printable lithium composition to provide a silicon anode with pores throughout the electrode created by lithium, for example diffusing from the printable lithium formulation.
- the porous silicon anode is formed by mixing the lithium powder, lithium particulates or printable lithium composition with a silicon active material in a slurry. The slurry may be coated onto a foil, mesh or foam. Solvent from the slurry is removed to form a dried anode, and the dried anode may then be pressed. Upon electrolyte addition, lithium intercalates or alloys with the negative electrode active material forming the porous silicon or silicon containing anode.
- the porous structure formed within the silicon anode mitigates volume expansion by providing a buffer to absorb the volume changes during subsequent electrochemical processing.
- the silicon anode formed by the silicon active material and the printable lithium composition has a porosity that may range between about 25% and 60%. In one embodiment, the porosity of the silicon anode is between about 30% and 50%. The porosity of an electrode may increase between about 5 to 15% when the electrode active material is prelithiated with a lithium source.
- the porosity for a non-prelithiated electrode may be determined by first subtracting the actual electrode density from its theoretical density, then dividing by the theoretical density.
- the electrode’s theoretical density is its true density for a perfect monolithic layer, but due to fraction of the volume of voids over the total volume, the actual density of an electrode will be lower than its theoretical density.
- subtracting the actual electrode density from its theoretical density indicates the electrode’s amount of vacant space between particles, and dividing the electrode’s vacant space by its theoretical density gives the electrode’s % porosity.
- Prelithiating an electrode may affect the electrode’s actual density and therefore its porosity.
- the actual density of a prelithiated electrode may be determined by first subtracting the contribution of lithium from the true density of each component to determine the electrode active material ratio and then multiplying the electrode active material’s ratio by its actual density for a non-prelithiated electrode. This is based on the assumption that all lithium is intercalated into the host active material and that after diffusion, pores would be left where lithium particles once resided. The porosity of the prelithiated electrode is then calculated by subtracting its actual density from the theoretical density of a non-prelithiated electrode, then dividing by the theoretical density.
- a porous conductive layer may also be formed on the surface of an anode during lithium diffusion.
- the printable lithium formulation may be applied to a pre fabricated silicon anode to create a porosity gradient electrode.
- the porosity of the lithium layer when the printable lithium composition is initially applied to the surface of a pre-fabricated surface may be expressed as:
- the theoretical density of a printable lithium composition is the sum of the true densities for each component multiplied by their respective mass percentages, wherein the total mass percentage is equal to one.
- the porosity of the lithium layer after diffusion into a pre-fabricated surface may be expressed as: [0042]
- the theoretical density of the printable lithium composition without lithium may be determined by dividing the sum of mass percentages for every component except lithium by the total volume of the printable lithium composition initially applied to the electrode surface. This assumes that all lithium from the printable lithium composition has diffused into the electrode.
- surfaces treated with a printable lithium composition after lithium diffusion have a higher porosity than the bulk electrode.
- the porosity at an electrode surface may be dependent on the amount of lithium deposited and diffused.
- Additives in the printable lithium formulation also increase conductivity on the surface and bulk of the electrode.
- the resultant porous, conductive gradient structure enables high rates of charging by lowering the effective areal current density and increasing surface and bulk conductivity, allowing for faster diffusion of lithium ions at the electrode surface and in the electrode bulk, thereby decreasing the likelihood of lithium plating on the anode surface.
- the faster diffusion kinetics results in lower charge transfer impedance and provides better charge rate capabilities.
- silicon anodes formed by silicon active material and a printable lithium composition may have an improvement in rate capability between about 5% and 30% at a 1C charge rate and between about 20% and 50% at a 2C charge rate compared to non- lithiated silicon anodes.
- Standard rechargeable Li-ion batteries require a formation process which usually takes several days to form a robust solid electrolyte interface (SEI) layer on the surface anode materials.
- SEI solid electrolyte interface
- the formation processes slow Li-ion batteries production rates and requires larger facility footprint and significant investment in formation equipment as described by An et al. (“Fast formation cycling for lithium ion batteries”, J Power Sources, 2017, 342, 846), incorporated herein by reference in its entirety.
- formation cycle time can be significantly decreased by prelithiating electrodes with a printable lithium composition.
- gas is generated during a standard SEI formation cycle due to solvent reduction during the formation of the SEI layer.
- Electrolyte solvents such as ethylene carbonate, may be reduced on the graphite surface at 2.7 V (-0.9 V vs Li/Li + ), which is well below the open circuit voltage of the cells prelithiated with a printable lithium composition, typically at 2.9-3V.
- cells with electrodes prelithiated with a printable lithium composition may produce almost no gas during a typical SEI formation charging-discharging cycle. This is because the SEI layer is formed on electrodes prelithiated with a printable lithium composition during a rest period prior to a formation cycle. Therefore, a simplified and shorter formation cycle can be used.
- the simplified formation process may only consist of a resting period of a few hours to up to 24 hours at room or elevated temperatures followed by a degassing process.
- FIG. 2A shows pouch cells with electrodes prelithiated with a printable lithium composition produce gas during the 24hs rest. This gas can be removed by a degassing step prior to formation cycle. In comparison, baseline cells, which are not prelithiated, do not produce gas during the 24hs rest.
- FIG. 2B shows baseline cells produced gas during the formation charging-discharging cycle while pouch cells with prelithiated electrodes produced no gas.
- FIG. 2C shows both baseline cells and cells containing printable lithium treated electrodes produce similar gas during long term cycling.
- the lithium source for lithiating a silicon or silicon-containing anode is a lithium metal powder.
- the lithium metal powder may be in the form of a finely divided powder.
- the lithium metal powder typically has a mean particle size of less than about 80 microns, often less than about 40 microns and sometimes less than about 20 microns.
- the lithium metal powder may be non-pyrophoric stabilized lithium metal power (SLMP®) available from FMC USA Lithium Corp.
- the lithium metal powder may also include a substantially continuous layer or coating of fluorine, wax, phosphorus or a polymer or the combination thereof (as disclosed in U.S. Pat. Nos. 5,567,474, 5,776,369, and 5,976,403 and incorporated herein by reference in their entireties). Lithium metal powder has a significantly reduced reaction with moisture and air.
- the lithium metal powder may also be alloyed with a metal.
- the lithium metal powder may be alloyed with a Group l-VIII element.
- Suitable elements from Group IB may include, for example, silver or gold.
- Suitable elements from Group MB may include, for example, zinc, cadmium, or mercury.
- Suitable elements from Group IIA of the Periodic Table may include beryllium, magnesium, calcium, strontium, barium, and radium.
- Elements from Group I IIA that may be used in the present invention may include, for example, boron, aluminum, gallium, indium, or thallium.
- Elements from Group IVA that may be used in the present invention may include, for example, carbon, silicon, germanium, tin, or lead.
- Elements from Group VA that may be used in the present invention may include, for example, nitrogen, phosphorus, or bismuth.
- Suitable elements from Group VIIIB may include, for example, palladium, or platinum.
- the lithium source is a printable lithium composition as described in US Application No. 16/359,707 and 16/573,587, which are incorporated herein by reference in their entireties.
- the printable lithium composition comprises a lithium metal powder, a polymer binder, a rheology modifier and may further include a solvent.
- the polymer binder is selected so as to be compatible with the lithium metal powder. “Compatible with” or “compatibility” is intended to convey that the polymer binder does not violently react with the lithium metal powder resulting in a safety hazard.
- the lithium metal powder and the polymer binder may react to form a lithium-polymer complex, however, such complex should be stable at various temperatures. It is recognized that the amount (concentration) of lithium and polymer binder contribute to the stability and reactivity.
- the polymer binder may have a molecular weight of about 1 ,000 to about 8,000,000, and often has a molecular weight of 2,000,000 to 5,000,000.
- Suitable polymer binders may include one or more of poly(ethylene oxide), polystyrene, polyisobutylene, natural rubbers, butadiene rubbers, styrene-butadiene rubber, polyisoprene rubbers, butyl rubbers, hydrogenated nitrile butadiene rubbers, epichlorohydrin rubbers, acrylate rubbers, silicon rubbers, nitrile rubbers, polyacrylic acid, polyvinylidene chloride, polyvinyl acetate, ethylene propylene diene termonomer, ethylene vinyl acetate copolymer, ethylene-propylene copolymers, ethylene-propylene terpolymers, polybutenes.
- the binder may also be a wax.
- the battery may further include a lithiation control layer.
- the polymer binder may form a film on the surface of the electrode to regulate the activation and lithiation rate of the electrode.
- the film formed by the polymer binder thus acts a pre-lithiation control layer, since lithium does not contact the electrode surface directly and lithiation is not likely to occur until electrolyte is added to the cell.
- the lithiation control layer may regulate lithium diffusion and slow the rate of dry state pre-lithiation that can occur during lamination of the lithium to the surface of the negative electrode and may subsequently allow for the dissipation of heat generation during storage of the electrode materials.
- a lithium control layer is described in US Publication No. 2019/0229380 herein incorporated by reference in its entirety. Having a controlled rate of lithium diffusion increases the safety of pre- lithiation process due to a controlled heat dissipation.
- the rheology modifier is selected so as to be compatible with the lithium metal powder and the polymer binder and dispersible in the composition.
- the rheology modifier is carbon-based.
- the rheology modifier may be comprised of carbon nanotubes to provide a structure for a coated electrode.
- carbon black may be added as a rheology modifier.
- a preferred embodiment of the printable lithium composition includes a carbon-based rheology modifier such as carbon nanotubes.
- a carbon-based rheology modifier such as carbon nanotubes.
- Use of carbon nanotubes may also provide a three-dimensional support structure and conductive network for a lithium anode when coated with the printable lithium composition and increase its surface area.
- Another support structure may be one as described by Cui et al. [Science Advances, Vol. 4, no. 7, page 5168, DOI:
- 10.1126/sciadv.aat5168 incorporated herein by reference in its entirety, which uses a hollow carbon sphere as a stable host that prevents parasitic reactions, resulting in improved cycling behavior.
- Yet another support structure may be a nanowire as described in US Patent No. 10,090,512 incorporated herein by reference in its entirety.
- Other compatible carbon-based rheology modifiers include carbon black, graphene, graphite, hard carbon and mixtures or blends thereof.
- Suitable rheology modifiers may include non-carbon-based materials, including titanium oxides and silicon oxides.
- silicon nanostructures such as nanotubes or nanoparticles may be added as a rheology modifier to provide a three-dimensional structure and/or added capacity.
- the rheology modifiers may also increase the durability of the layer (i.e., coating, foil or film) formed from the printable lithium composition by preventing mechanical degradation and allow for faster charging.
- Additional rheology modifiers may be added to the composition to modify properties such as viscosity and flow under shear conditions.
- the rheology modifier may also provide conductivity, improved capacity and/or improved stability/safety depending on the selection of the rheology modifier.
- the rheology modifier may be the combination of two or more compounds so as to provide different properties or to provide additive properties.
- Exemplary rheology modifiers may include one or more of silicon nanotubes, fumed silica, titanium dioxide, zirconium dioxide and other Group IIA, IMA, IVB, VB and VIA elements/compounds and mixtures or blends thereof.
- additives intended to increase lithium ion conductivity can be used; for example, electrochemical device electrolyte salts such as lithium perchlorate (UCIO4), lithium hexafluorophosphate (LiPFe), lithium difluoro(oxalate)borate (LiDFOB), lithium tetrafluoroborate (L1BF4), lithium nitrate (L1NO3), lithium bis(oxalate) borate (LiBOB), lithium trifluoromethanesulfonimide (LiTFSI), lithium bis(fluorosulfonyl) imide (LiFSI).
- the additives included in the printable lithium formulation may also be selected to modify the porosity and overall three-dimensional support structure as desired. Examples may include carbon nanotubes (CNTs), graphene or polyacrylate as described in Electrochemical and Solid-State Letters, 12, 5, A107-A110, 2009.
- Solvents compatible with lithium may include acyclic hydrocarbons, cyclic hydrocarbons, aromatic hydrocarbons, symmetrical ethers, unsymmetrical ethers, cyclic ethers, alkanes, sulfones, mineral oil, and mixtures, blends or cosolvents thereof.
- suitable acyclic and cyclic hydrocarbons include n-hexane, n-heptane, cyclohexane, and the like.
- suitable aromatic hydrocarbons include toluene, ethylbenzene, xylene, isopropylbenzene (cumene), and the like.
- Suitable symmetrical, unsymmetrical and cyclic ethers include di-n-butyl ether, methyl t-butyl ether, tetrahydrofuran, glymes and the like.
- Commercially available isoparaffinic synthetic hydrocarbon solvents with tailored boiling point ranges such as Shell Sol® (Shell Chemicals) or Isopar® (Exxon) are also suitable.
- the polymer binder and solvents are selected to be compatible with each other and with the lithium metal powder.
- the binder or solvent should be non-reactive with the lithium metal powder or in amounts so that any reaction is kept to a minimum and violent reactions are avoided.
- the binder and solvent should be compatible with each other at the temperatures at which the printable lithium composition is made and will be used.
- the solvent (or co-solvent) will have sufficient volatility to readily evaporate from the printable lithium composition (e.g., in slurry form) to provide drying of the printable lithium composition (slurry) after application.
- a mixture of the polymer binder, rheology modifier, coating reagents, and other potential additives for the lithium metal powder may be formed and introduced to contact the lithium droplets during dispersion at a temperature above the lithium melting point, or at a lower temperature after the lithium dispersion has cooled such as described in U.S. Patent No. 7,588,623 the disclosure of which is incorporated by reference in its entirety.
- the thusly modified lithium metal may be introduced in a dry powder form or in a solution form in a solvent of choice. It is understood that combinations of different process parameters could be used to achieve specific coating and lithium powder characteristics for particular applications.
- the components of the printable lithium composition may be mixed together as a slurry or paste to have a high concentration of solid.
- the slurry/paste may be in the form of a concentrate with not all of the solvent necessarily added prior to the time of depositing or applying.
- the lithium metal powder should be uniformly suspended in the solvent so that when applied or deposited a substantially uniform distribution of lithium metal powder is deposited or applied. Dry lithium powder may be dispersed such as by agitating or stirring vigorously to apply high sheer forces.
- a mixture of the polymer binder, rheology modifier, coating reagents, and other potential additives for the lithium metal powder may be formed and introduced to contact the lithium droplets during the dispersion at a temperature above the lithium melting point, or at a lower temperature after the lithium dispersion has cooled such as described in U.S. Patent No. 7,588,623 the disclosure of which is incorporated by reference in its entirety.
- the thusly modified lithium metal may be introduced in a dry powder form or in a solution form in a solvent of choice. It is understood that combinations of different process parameters could be used to achieve specific coating and lithium powder characteristics for particular applications.
- the printable lithium composition may comprise between about 50% to about 98% by weight of lithium metal powder and about 2% to about 50% by weight of polymer binder and rheology modifiers on a dry weight basis. In one embodiment, the printable lithium composition comprises between about 60% to about 90% by weight lithium metal powder and between about 10% to about 40% by weight of polymer binder and rheology modifiers. In another embodiment the printable lithium composition comprises between about 75% to about 85% by weight of lithium metal powder and between about 15% to about 30% by weight of polymer binder and rheology modifiers.
- An important aspect of printable lithium compositions is the rheological stability of the suspension. Because lithium metal has a low density of 0.534 g/cc, it is difficult to prevent lithium powder from separating from solvent suspensions.
- viscosity and rheology may be tailored to create the stable suspension of the invention.
- a preferred embodiment shows no separation at greater than 90 days. This may be achieved by designing compositions with zero shear viscosity in the range of 1 x 10 4 cps to 1 x 10 7 cps, wherein such zero shear viscosity maintains the lithium in suspension particularly when in storage. When shear is applied, the suspension viscosity decreases to levels suitable for use in printing or coating applications.
- the resulting printable lithium composition preferably may have a viscosity at 10s 1 about 20 to about 20,000 cps, and sometimes a viscosity of about 100 to about 2,000 cps, and often a viscosity of about 700 to about 1,100 cps. At such viscosity, the printable lithium composition is a flowable suspension or gel.
- the printable lithium composition preferably has an extended shelf life at room temperature and is stable against metallic lithium loss at temperatures up to 60°C, often up to 120°C, and sometimes up to 180°C.
- the printable lithium composition may separate somewhat over time but can be placed back into suspension by mild agitation and/or application of heat.
- the printable lithium composition comprises on a solution basis about 5 to 50 percent lithium metal powder, about 0.1 to 20 percent polymer binder, about 0.1 to 30 percent rheology modifier and about 50 to 95 percent solvent. In one embodiment, the printable lithium composition comprises on a solution basis about 15 to 25 percent lithium metal powder, about 0.3 to 0.6 percent polymer binder having a molecular weight of 4,700,000, about 0.5 to 0.9 percent rheology modifier, and about 75 to 85 percent solvent.
- the lithium source is applied onto a surface of an anode to form a porous conductive layer on the surface during lithium diffusion.
- the lithium source may be a lithium metal powder or a printable lithium composition.
- the printable lithium composition may have a slower lithium diffusion rate than other lithium sources during prelithiation due to the polymer layer applied to the surface during application of the printable lithium composition.
- the rate of diffusion may decrease by about half for lithium deposited as a printable lithium composition.
- High heat generation caused by rapid diffusion in the dry state may damage the electrode or cause fires while the electrode roll is stored prior to slitting and final cell assembly.
- the slower diffusion rate may provide a safer prelithation process because of a slower rate of heat generated during the diffusion process thus more time for dissipation of heat.
- a current collector, electrode and/or solid electrolyte of the solid-state battery may comprise a substrate coated with a printable lithium composition as described in US Application Nos. 16/573,556, 16/359,733 and 16/573,587, all of which are herein incorporated by reference in their entireties.
- the battery may include a cathode, an electrolyte and a porous anode lithiated with the printable lithium composition.
- the electrolyte may have a concentration of above 1 M, often equal to about 3 M or higher, and sometimes above 5 M.
- Suitable electrolytes include lithium perchlorate (LiCICU), lithium hexafluorophosphate (LiPFe), lithium difluoro(oxalate)borate (LiDFOB), lithium tetrafluoroborate (L1BF4), lithium nitrate (UNO 3 ), lithium bis(oxalate) borate (LiBOB), lithium bis(fluorosulfonyl) imide (LiFSI) and lithium trifluoromethanesulfonimide (LiTFSI) and mixtures or blends thereof.
- LiCICU lithium perchlorate
- LiPFe lithium hexafluorophosphate
- LiDFOB lithium difluoro(oxalate)borate
- Li1BF4 lithium tetrafluoroborate
- L1BF4 lithium nitrate
- LiBOB lithium bis(oxalate) borate
- LiFSI lithium bis(fluorosulfonyl) imide
- LiTFSI lithium tri
- One exemplary example is a battery having a cathode and a porous anode lithiated with a printable lithium composition and a high concentration electrolyte, wherein LiFSI is the major salt of the high concentration electrolyte.
- Another example is a battery having a cathode and a porous anode lithiated with a printable lithium composition and a dual-salt liquid electrolyte as described by Weber et al [Nature Energy, Vol. 4, pgs. 683-689 (2019), DOI: 10.1038/s41560-019-0428-9] and US Publication No. 2019/0036171, both of which are incorporated herein by reference.
- the dual salt liquid electrolyte may be comprised of lithium difluoro(oxalate)borate (LiDFOB) and UBF4, and may have a concentration of about 1 M. Dual-salt electrolytes may provide increased initial capacity retentions and improved cycle performance.
- the current collector material may be a foil, mesh or foam.
- the anode material may comprise graphite, hard carbon, graphite-SiOx composite, SiOx, SiO, S1O2, SiC,
- Si, Si/C composite, Si-based alloys, graphite-SnO, Sn/C composite, and other lithium ion battery and lithium ion capacitor anode materials Since it has hole across the substrate, mesh is used to improve the energy density of the batteries by reducing the weight of current collector. Foam may also be used as a current collector. Continuous 3D-form can provide a special porous structure which will help to accommodate more Li + , hence hindering the growth of Li dendrites, improving the rate capability and extending the cycle life.
- the active anode material and the printable lithium composition are provided together and extruded onto the current collector (e.g., copper, nickel, etc.).
- the active anode material and printable lithium composition may be mixed and co extruded together.
- active anode materials include graphite, graphite-SiO, graphite- SnO, SiO, hard carbon and other lithium ion battery and lithium ion capacitor anode materials.
- the active anode material and the printable lithium composition are co extruded to form a layer of the printable lithium composition on the current collector.
- the deposition of the printable lithium composition including the above extrusion technique may include depositing as wide variety patterns (e.g., dots, stripes), thicknesses, widths, etc.
- the printable lithium composition and active anode material may be deposited as a series of stripes, such as described in US Publication No. 2014/0186519 incorporated herein by reference in its entirety.
- the stripes would form a 3D structure that would account for expansion of the active anode material during lithiation.
- silicon may expand by 300 to 400 percent during lithiation. Such swelling potentially adversely affects the anode and its performance.
- the silicon anode material can expand in the X-plane alleviating electrochemical grinding and loss of particle electrical contact.
- the printing method can provide a buffer for expansion.
- the printable lithium formulation is used to form the anode, it could be co-extruded in a layered fashion along with the cathode and separator, resulting in a solid-state battery.
- the anode may comprise a partially lithium-loaded silicon-based active material as described in US Publication No. 2018/0269471 herein incorporated by reference in its entirety, in which the partially loaded active material has a selected degree of loading of lithium through intercalation/alloying or the like.
- the anode active material may be mechanically lithiated with a printable lithium composition.
- the anode active material may be pressed with force selected to induce mechanical lithiation once a printable lithium composition is applied on its surface.
- the printable lithium composition may be incorporated into a three- dimensional electrode structure as described in US Publication No. 2018/0013126 herein incorporated by reference in its entirety.
- the printable lithium composition may be incorporated into a three-dimensional porous anode, porous current collector or porous polymer or ceramic film, wherein the printable lithium composition may be deposited therein.
- the printable lithium composition may be incorporated into a solid electrolyte, wherein the solid electrolyte may be combined with or applied to a lithium metal anode to form a composite anode.
- the solid electrolyte may be applied as one or more interface ion conductive electrolyte layers or interfaces to the lithium metal anode.
- One example is described in US Patent No. 8,182,943 herein incorporated by reference in its entirety.
- the printable lithium composition may be incorporated into a three-dimensional electrode structure as described in US Publication No. 2018/0013126 herein incorporated by reference in its entirety.
- the three-dimensional electrode may be a permeable composite material comprised of a support defining pores and an alkali metal deposit on the support, wherein the alkali metal is deposited using a printable lithium composition.
- the three- dimensional electrode may have a porosity between about 1% by volume to about 95% by volume, and may have a mean flow pore size in the range of from about 1 nm to about 300 pm.
- Another embodiment of the battery may include a composite anode formed using a pulsed electron beam as described in US Patent No.
- the pulsed electron beam may be used as a virtual cathode deposition (VCD) process applied to an anode material, wherein a three-dimensional porous anode structure is created using the electron beam.
- VCD virtual cathode deposition
- the three-dimensional structure formed from the pulsed electron beam may be a carbon allotrope for lithium ion batteries (CALIB).
- the CALIB structure may be deposited with lithium using a printable lithium composition to form a carbon polymorph.
- an electrode prelithiated with the printable lithium composition can be assembled into a cell with the electrode to be preloaded with lithium.
- a separator can be placed between the respective electrodes.
- Current can be allowed to flow between the electrodes.
- an anode prelithiated with the printable lithium composition of the present invention may be formed into a second battery such as described in U.S. Patent No. 6,706,447 herein incorporated by reference in its entirety.
- the cathode is formed of an active material, which is typically combined with a carbonaceous material and a binder polymer.
- the active material used in the cathode is preferably a material that can be lithiated.
- non-lithiated materials such as MnC> 2 , V 2 O 5, M0S 2 , metal fluorides or mixtures thereof, Sulphur and sulfur composites can be used as the active material.
- lithiated materials such as LiM ⁇ CU and UMO 2 wherein M is Ni,
- Co or Mn that can be further lithiated can also be used.
- the non-lithiated active materials are preferred because they generally have higher specific capacities, lower cost and broader choice of cathode materials in this construction that can provide increased energy and power over conventional secondary batteries that include lithiated active materials.
- the printable lithium composition may be used to form a monolithic lithium metal anode of various thicknesses and widths for use in a solid-state battery, including solid- state batteries as described in US Patent Nos. 8,252,438 and 9,893,379 and incorporated herein by reference in their entireties.
- the printable lithium composition may be applied or deposited so as to form a solid electrolyte for a solid-state battery, and includes combining the printable lithium composition with a polymer or ceramic material to form a solid electrolyte.
- the surfaces of typical solid electrolytes may be rough depending on the solid electrolyte selection and therefore may not form good contacts between the solid electrolyte and the lithium (foil) anode, leading to a sub-optimal interface and reduced battery performance.
- the printable lithium composition may be used to prelithiate a solid electrolyte, forming an interface layer that improves the solid electrolyte surface and therefore provides for improved adhesion with a lithium anode.
- the interface layer may comprise a foil or film formed from a printable lithium composition. The printable lithium composition forming the interface layer may be applied to various types of solid electrolytes, including polymer, glass, and ceramic electrolytes.
- Having a modified solid electrolyte surface optimizes contact between the solid electrolyte and a lithium anode, resulting in an improved interface between the solid electrolyte and lithium anode and leading to better battery performance by lessening the impedance growth caused by loss of contact between lithium and the electrolyte that occurs because of volume increase of the lithium during cycling.
- a solid-state secondary battery may include a cathode capable of electrochemically absorbing and desorbing lithium; an anode capable of electrochemically absorbing and desorbing lithium, the anode including an active material layer that comprises an active material, the active material layer being carried on a current collector; and a non-aqueous electrolyte as described in US Patent No. 7,914,930 herein incorporated by reference in its entirety.
- a method includes the steps of: reacting lithium with the active material of the anode by bringing the printable lithium composition into contact with a surface of the active material layer of the anode; and thereafter combining the anode with the cathode to form an electrode assembly.
- 17g artificial graphite, 2g SiO and 12.5g of 8% styrene butadiene rubber in toluene are combined with 8.5g toluene in a 250ml polypropylene cup.
- the mixture is blended at lOOOrpm for 3 minutes in a THINKY ARE 250 planetary centrifugal mixer creating a uniform anode slurry.
- 0.85g of stabilized lithium metal powder (SLMP®, FMC USA Lithium Corp.) or PLF with equivalent lithium metal content is added to the slurry and blended in the THINKY for 30 seconds at lOOOrpm.
- the resulting slurry is coated on copper foil using a 6mil doctor blade.
- the solvent is dried using a forced hot air dryer at 110°C until all solvent is removed.
- the dried electrode is pressed using at 30pm gap roll press.
- a 4cm x 4cm piece of the pressed electrode is placed into a sealed pouch with 1g of 1M LiPF 6 in EC/DEC 1:1 electrolyte and observed under a digital microscope.
- Theoretical density is calculated by subtracting the contribution of lithium from the true density of each component, based on the assumption that all lithium is intercalated into the host anode material and that after diffusion pores would be left where lithium particles once resided.
- Anode electrodes from LiFun Technologies are used to test the effectiveness of printable lithium formulation to increase first cycle efficiency (FCE). Electrodes containing 10% SiO are used for testing.
- the formulation for 10% SiO anode electrode comprises 85.32% artificial graphite + 9.48% SiO, 3.8% binder (CMC + SBR) and 1.4% carbon black.
- the loading of the anode materials is 8.2mg/cm 2 and the press density is about 1.5g/cm 3 .
- the size of the electrode is 7cm x 7cm. This anode electrode has an FCE of 85% when tested in a half cell with a lithium metal counter electrode.
- printable lithium formulation containing 6mg of stabilized lithium metal powder (SLMP®, FMC USA Lithium Corp.) is applied to the surface of the 10% SiO electrode. After drying and pressing, the electrode is assembled into a half cell in the pouch cell format with lithium metal counter electrode using 1M LiPF 6 in EC:FEC:EMC:DMC 1 : 1 :2:6 (volume ratio) electrolyte. The cell is tested with the following protocol on a Maccor series 4000 cycler: Rest 24hrs @ 45°C, then 1 Cycle conducted at the following condition: 1) discharge at 0.1C to 0.005V, 2) a constant voltage step until current drop to 0.05C, 3) charge at 0.1 C to 1 5V.
- SLMP® stabilized lithium metal powder
- FIGS. 1 A and 1 B show the as-printed, dried and pressed formulation on the surface of the 10% SiO containing graphite electrode and the resulting increase in surface porosity after lithium diffusion.
- Baseline (BL) and cells containing PLF-incorporated electrodes single-layer pouch cells are made with NMC 811 cathode and Graphite -10% SiO with Celgard 3501 separator. 1g of 1M LiPF 6 in 1 :1 :2:6 Vol EC: FEC: EMC: DMC electrolyte is used. Cells are cycled using the formation protocol of a 24-hour rest period at a temperature of 45°C, followed by charging at the constant current of 10 mA to 4.2V and then discharging at the constant current of 10 mA to 2.8V with a current cutoff of 5 mA. The cells are charged to 3.8V after formation step for impedance measurements. Following initial impedance test, the cells are tested for rate capability.
- Surface porosity for the PLF cells is about 50% prior to lithium diffusion. Lithium represents about 84% of the volume of the PLF treatment solution. After lithium diffusion, the surface porosity is about 88.5% and the porosity of the bulk is 34%. Increased porosity at the surface provides increased surface area for electrolyte absorption and therefore faster lithium ion diffusion kinetics. Faster diffusion kinetics results in lower charge transfer impedance and provides better charge rate capabilities.
- FIGS. 2A-C are plots comparing gas generation for between baseline and PLF-treated NMC811/Graphite-5%SiO pouch cells during a) 24 hours rest at 60°C; b) first two formation cycles and c) cycling at room temperature. Gas generation is indicative of SEI formation.
- PLF-incorporated cells produced the most gas during 24 hours rest at 60°C.
- baseline cells produced no gas during the same period of rest time.
- FIGS. 2A-C demonstrate the PLF-incorporated cells are capable of producing a SEI layer within a shorter period of time compared to baseline cells.
- FIG. 2B shows the gas production differences between baseline and PLF-incorporated NMC811/Graphite-5%SiO pouch cells during the first 2 cycles.
- PLF-incorporated cells produced almost no gas while baseline cells produced gas during the formation cycle. This is because the SEI formation for baseline cells occurs below 3V where most of the solvent is reduced on anode surface.
- PLF-incorporated cells form the SEI layer during the 24 hours rest period and therefore no formation cycle is needed to form SEI layers with PLF- treated cells.
- FIG. 2C shows gas production comparison between baseline and PLF-incorporated NMC811/Graphite-5%SiO pouch cells during 1C rate cycling at room temperature (RT) measured at the end of cycle life (20% capacity loss). Both baseline and PLF-incorporated cells produced a similar volume of gas.
- PLF diffusion rate is 30% slower than when using SLMP alone.
- the diffusion rate is slowed by the polymer layer applied to the surface of the anode during PLF application. This slower diffusion rate can result in controlled heat dissipation during the diffusion process and leads to a safer prelithiation process.
- PLF diffusion is minimal compared to use of dry SLMP. This property leads to less heat generation due to lithium diffusion after lamination of PLF to the electrode surface. Heat generation due to dry state lithium diffusion in electrode rolls during storage has been observed to generate heat sufficient to damage the electrode films or even cause thermal event while the electrode rolls are stored prior to being used in cell assembly processes.
- FIG. 3 shows a comparison of the diffusion rate of lithium, deposited as SLMP compared to the diffusion rate of lithium deposited as a printable lithium composition, into a SiO anode material in the dry state.
- the electrodes are treated with either SLMP or PLF at a loading equal to about 0.7mg/cm 2 lithium, a quantity sufficient to compensate the irreversible capacity.
- the electrodes are then pressed with force selected to induce mechanical lithiation.
- the test results show that the diffusion rate of lithium deposited using PLF is significantly slower than that of SLMP.
- FIG. 4 shows the differential capacity (dQ/dV) versus potential (V) curves for baseline cells and PLF-incorporated cells. As seen in FIG.
- the baseline cells have a pronounced peak at 2.7 V, which is due to the reduction of Fluoroethylene Carbonate on the graphite surface, and a peak at 2.9 V, which is due to the well-known reduction of Ethylene Carbonate on anode surface.
- FIG. 4 shows that PLF-treated cells have no solvent reduction peaks at all during the formation cycle before 2.9 V. This is because pre-lithiation treatment results in partial charging of the cell higher than 2.9 V. This voltage is beyond the voltage of solvent reduction, indicating that direct anode contacts with Li metal initiates SEI layer formation during the pre- lithiation process.
- FIGS. 5A and 5B compare the AC impedances between baseline and PLF-incorporated NMC811/Graphite-5%SiO pouch cells measured after two formation cycles and after cycling.
- FIGS. 5A and 5B show PLF-incorporated cells have significantly lower impedance after formation and during cycling, indicating that treating cells with printable lithium compositions may improve the rate performance. As reported in Table 1, PLF-incorporated cells may have an improved cycle efficiency compared to baseline lithium ion cell.
- Table 4 compares various features between baseline cells and printable lithium incorporated cells. There is about a 5% thickness increase after cell assembly in NMC811/Graphite-5%SiO for PLF incorporated cells versus baseline cells. Each double side treated anode electrode has about a 10 pm thickness increase, thus the 10-layer cells have about 100 pm total increase in thickness as assembled. However, during formation, all deposited lithium will intercalate into the bulk of the anode resulting in no apparent thickness change between treated and baseline pouch cells. The cell volume measurements indicate no increase after formation as well. There is an increase in first cycle discharge capacity resulting in 7% higher first cycle efficiency for the cells incorporating anodes treated with a printable lithium composition. The volumetric and gravimetric energy density increased about 11% and 10%, respectively, for the PLF-incorporated cells.
- the gas production data in FIGS. 2A-C and the voltage data in FIG. 4 indicate that the SEI layer for PLF-incorporated cells is being formed during the rest step.
- the benefit is that the formation cycle for PLF-incorporated cells may be eliminated or drastically reduced.
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