Patent Application
20240162479
Batteries can have different power capacities to charge and discharge power to operate machines.
If exposed directly at the electrode surface in contact with liquid electrolytes, manganese from manganese-containing cathodes can dissolve (in Mn2+(aq.) form), and further react to form manganese metal (Mn0) at the anode, leading to degradation of the battery. Thus there remains a need for apparatuses, systems, and methods that may improve performance of cells comprising manganese-containing cathodes.
At least one aspect is directed to a battery cell. The battery cell can include a component. The battery can include a metal fluoride MxFy disposed in the component, where M is a metal element different from Mn (such as Li, K, Ba, Ca, Na, La, Y, Mg, Ce, or Al), 1<x≤3 and 1≤y≤3. In some aspects, metal fluoride MxFy is one or more of KF, BaF2, and NaF. In some aspects, the component comprises an electrolyte and MxFy is present in the electrolyte. In some aspects, the component comprises an anode and MxFy is coated on the anode. In some aspects, the component comprises an anode and MxFy is incorporated in the anode. In some aspects where the component comprises a coating or an additive, the coating or the additive comprises less than 5 wt % of MxFy.
In accordance with any of the foregoing aspects, the battery cell may comprise a solid electrolyte interphase, and an amount of Mn0 in the solid electrolyte interphase may be less than an amount of Mn0 in a solid electrolyte interphase of a battery cell without MxFy. In accordance with any of the foregoing aspects, the battery cell may comprise a solid electrolyte interphase, and the solid electrolyte interphase may comprise a ternary Mn2+-containing metal fluoride compound formed by a reaction between MxFy and MnF2. In some aspects, an amount of the ternary metal fluoride compound in the solid electrolyte interphase is greater than an amount of ternary metal fluoride compound in a solid electrolyte interphase of a battery cell without MxFy. Additionally or alternatively, in accordance with any of the foregoing aspects, Mn dissolution from a Mn-containing cathode may form a ternary Mn2+-containing metal fluoride compound by a reaction between MxFy and Mn from the Mn-containing cathode.
At least one aspect is directed to an electrode. The electrode can include an anode active material. The electrode can include a solid electrolyte interphase on the anode active material. The solid electrolyte interphase can include MxMn(O1-yFy)z, where M is a metal element different from Mn (such as Li, K, Ba, Ca, Na, La, Y, Mg, Ce, or Al), x≥1, 0≤y≤1, and z≥3. In some aspects, MxMn(O1-yFy)z comprises Mx1Mn(O1-yFy)z and the anode active material further comprises Ma2Fb, wherein 1≤a≤3 and 1≤b≤3. In some aspects, M1 is selected from K, Na, and Ba. In some aspects M2 is selected from Li, K, Ba, Ca, Na, La, Y, Mg, Ce, and Al. In some aspects, MxMn(O1-yFy)z is one or more of K2MnF4, KMnF3, BaMnF4, and NaMnF3, and their oxyfluoride compounds (O1-yFy). In some aspects, MxMn(O1-yFy)z is one or more of K2MnF4, KMnF3, BaMnF4, and NaMnF3.
At least one aspect is directed to a method. The method can include disposing MxFy in a component of a battery cell, where M is a metal element different from Mn (such as Li, K, Ba, Ca, Na, La, Y, Mg, Ce, or Al), 1≤x≤3 and 1≤y≤3. In some aspects, MxFy is one or more of KF, BaF2, and NaF. In some aspects, the component comprises an electrolyte and the method comprises disposing MxFy in the electrolyte. In some aspects, the component comprises an anode and the method comprises providing a coating comprising MxFy on the anode. In some aspects, the component comprises an anode and the method comprises incorporating MxFy in the anode. In some aspects where the component comprises a coating or an additive, the coating or the additive comprises less than 5 wt % of MxFy.
At least one aspect is directed to an electric vehicle. The electric vehicle can include a battery. The battery can include a component. The battery can include MxFy disposed in the component, where M is a metal element different from Mn (such as Li, K, Ba, Ca, Na, La, Y, Mg, Ce, or Al), and 1≤x≤3 and 1≤y≤3. In some aspects, MxFy is one or more of KF, BaF2, and NaF.
At least one aspect is directed to an electric vehicle. The electric vehicle can include a battery. The battery can include an electrode. The electrode can include an anode active material. The electrode can include a solid electrolyte interphase (SEI) on the anode active material. The solid electrolyte interphase can include MxMn(O1-yFy)z, where M is a metal different from Mn (such as Li, K, Ba, Ca, Na, La, Y, Mg, Ce, or Al), x≥1, 0≤y≤1, and z≥3. In some aspects, MxMn(O1-yFy)z is one or more of K2MnF4, KMnF3, BaMnF4, NaMnF3, and their oxyfluoride compounds (O1-yFy).
At least one aspect is directed to a system. The system can include a battery. The battery can include a component. The battery can include MxFy disposed in the component where M is a metal different from Mn (such as Li, K, Ba, Ca, Na, La, Y, Mg, Ce, or Al), 1≤x≤3 and 1≤y≤3. In some aspects, MxFy is one or more of KF, BaF2, and NaF.
At least one aspect is directed to a system. The system can include an electrode. The electrode can include an anode active material. The electrode can include a solid electrolyte interphase on the anode active material. The solid electrolyte interphase can include MxMn(O1-yFy)z, where M is a metal different from Mn (such as Li, K, Ba, Ca, Na, La, Y, Mg, Ce, or Al), and x≥1, 0≤y≤1, and z≥3. In some aspects, MxMn(O1-yFy)z is one or more of K2MnF4, KMnF3, BaMnF4, and NaMnF3, and their oxyfluoride compounds (O1-yFy).
These and other aspects and implementations are discussed in detail below. The foregoing information and the following detailed description include illustrative examples of various aspects and implementations, and provide an overview or framework for understanding the nature and character of the apparatuses, systems and methods disclosed herein. The drawings provide illustration and a further understanding of the various aspects and implementations, and are incorporated in and constitute a part of this disclosure. The foregoing information and the following detailed description and drawings include illustrative examples and should not be considered as limiting.
The accompanying drawings are not intended to be drawn to scale. Like reference numbers and designations in the various drawings indicate like elements. For purposes of clarity, not every component may be labeled in every drawing. In the drawings:
Following below are more detailed descriptions of various concepts related to, and implementations of, methods, apparatuses, and systems of reducing or preventing manganese metal formation. The various concepts introduced above and discussed in greater detail below may be implemented in any of numerous ways.
The present disclosure is directed to apparatuses, systems and methods of reducing or preventing manganese metal formation in a battery. Manganese from manganese-containing cathodes can dissolve in Mn2+(aq.) form in liquid electrolytes, and react to form manganese metal (Mn0) at the anode, leading to degradation of the battery. For example, dissolved manganese ions can react with HF present in an electrolyte to form MnF2 in a solid electrolyte interphase of a battery, and further reduction of MnF2 within the electrochemical cell can lead to manganese metal formation and deposition at the anode. Such manganese metal can increase the polarization of the anode and increase the impedance resistance of the battery. This problem may arise in any battery comprising a Mn-containing cathode. Because the problem stems from dissolution of Mn2+, the problem may particularly arise in a battery comprising a Mn2+-containing cathode. The problem also may arise in a battery comprising a Mn3+-containing cathode, where the Mn3+ is subject to disproportionation reaction to Mn2+ and Mn4+. A continuous electrochemical reduction of a Mn4+-containing cathode, Mn4+ may electrochemically reduce to Mn3+. Mn4*is generally a more stable species in such batteries under typical operating conditions, as compared to either Mn2+ or Mn3+ cathodes. Thus, in some aspects, the battery comprises a LiMnaFe1-aPO4 (LMFP) cathode, where 0≤a≤1. In an LMFP cathode, Mn metal has an oxidation state of 2+. In some aspects, the battery comprises a LiMn2O4 cathode. In a LiMn2O4 cathode, Mn metal has an oxidation state of 3+ and 4+. In some aspects, the battery comprises a Li(NibCocMn1-b-c)O2 (NMC or NMCA) cathode. In NMC or NMCA (A is Aluminum), most Mn metal has an oxidation state of 4+.
Addressing this problem, a technical solution described herein is a battery cell including a binary fluoride Mn2+ scavenging species disposed in a component. The binary fluoride Mn2+ scavenging species may be a metal fluoride species MxFy, where M is a metal different from Mn (such as Li, K, Ba, Ca, Na, La, Y, Mg, Ce, or Al), and 1≤x≤3 and 1≤y≤3. In specific aspects, M is K, Ba, or Na. In further specific aspects, MxFy is one or more of KF, BaF2, and NaF. In some embodiments, a fraction of the fluorine is doped or substituted by oxygen.
The binary fluoride Mn2+ scavenging species may react with Mn2+ to form a stable Mn2+-containing ternary species (Mn-M-F). Without a scavenging species as described herein, Mn2+ ions move to, e.g., a graphite anode, and react to form MnF2, which may be deposited at the anode surface. The stable Mn2+-containing ternary species (Mn-M-F) may be deposited at the anode. Specifically, use of the binary fluoride Mn2+ scavenging species as described herein may lead to the formation of MxMn(O1-yFy)z (e.g., at the anode), where x≥1, 0≤y≤1, and z≥3. In specific aspects, MxMn(O1-yFy)z is one or more of K2MnF4, KMnF3, BaMnF4, and NaMnF3. MxMn(O1-yFy)z can be one or more of oxyfluoride compounds (O1-yFy) of K2MnF4, KMnF3, BaMnF4, and NaMnF3. In some embodiments, a fraction of fluorine can be doped or substituted by oxygen. For example, with an electrode including an anode active material, wherein the electrode includes a solid electrolyte interphase (SEI) on the anode active material, the solid electrolyte interphase (SEI) may include MxMn(O1-yFy)z, where M is a metal different from Mn, and x≥1, 0≤y≤1, and z≥3.
The disclosed solutions have a technical advantage of reducing or preventing manganese metal formation in the battery cell. The solutions can decrease the cell polarization coming from the anode and decrease the overall impedance resistance of the battery. The solutions can reduce or prevent decrease of battery capacity over time. The solution can reduce or prevent the sudden drop in battery power capability (e.g., smooth acceleration in electric vehicle). The solutions can reduce or decrease the thermodynamic tendency for manganese metal formation. Further details are discussed and illustrated below with reference to the drawings.
The battery modules 115 can each include a plurality of battery cells 120. The battery modules 115 can be disposed within the housing 205 of the battery pack 110. The battery modules 115 can include battery cells 120 that are cylindrical cells or prismatic cells, for example. The battery module 115 can operate as a modular unit of battery cells 120. For example, a battery module 115 can collect current or electrical power from the battery cells 120 that are included in the battery module 115 and can provide the current or electrical power as output from the battery pack 110. The battery pack 110 can include any number of battery modules 115. For example, the battery pack can have one, two, three, four, five, six, seven, eight, nine, ten, eleven, twelve or other number of battery modules 115 disposed in the housing 205. It should also be noted that each battery module 115 may include a top submodule 220 and a bottom submodule 225, possibly with a thermal component 215 in between the top submodule 220 and the bottom submodule 225. The battery pack 110 can include or define a plurality of areas for positioning of the battery module 115 and/or cells 120. The battery modules 115 can be square, rectangular, circular, triangular, symmetrical, or asymmetrical. In some examples, battery modules 115 may be different shapes, such that some battery modules 115 are rectangular but other battery modules 115 are square shaped, among other possibilities. The battery module 115 can include or define a plurality of slots, holders, or containers for a plurality of battery cells 120. It should be noted the illustrations and descriptions herein are provided for example purposes and should not be interpreted as limiting. For example, the battery cells 120 can be inserted in the battery pack 110 without battery modules 220 and 225. The battery cells 120 can be disposed in the battery pack 110 in a cell-to-pack configuration without modules 220 and 225, among other possibilities.
Battery cells 120 have a variety of form factors, shapes, or sizes. For example, battery cells 120 can have a cylindrical, rectangular, square, cubic, flat, pouch, elongated or prismatic form factor. As depicted in
For example, the battery cell 120 can include at least one lithium-ion battery cell. In lithium-ion battery cells, lithium ions can transfer between a positive electrode and a negative electrode during charging and discharging of the battery cell. For example, the battery cell anode can include lithium or graphite, and the battery cell cathode can include a lithium-based oxide material. The electrolyte material can be disposed in the battery cell 120 to separate the anode and cathode from each other and to facilitate transfer of lithium ions between the anode and cathode. It should be noted that battery cell 120 can also take the form of a solid state battery cell developed using solid electrodes and solid electrolytes. Solid electrodes or electrolytes can be or include inorganic solid electrolyte materials (e.g., oxides, sulfides, phosphides, ceramics), solid polymer electrolyte materials, hybrid solid state electrolytes, or any combination thereof. In some implementations, the solid electrolyte layer can include polyanionic or oxide-based electrolyte material (e.g., Lithium Superionic Conductors (LISICONs), Sodium Superionic Conductors (NASICONs), perovskites with formula ABO3 (A=Li, Ca, Sr, La, and B=Al, Ti), garnet-type with formula A3B2(XO4)3(A=Ca, Sr, Ba and X=Nb, Ta), lithium phosphorous oxy-nitride (LixPOyNz). In some implementations, the solid electrolyte layer can include a glassy, ceramic and/or crystalline sulfide-based electrolyte (e.g., Li3PS4, Li7P3S11, Li2S—P2S5, Li2S—B2S3, SnS—P2S5, Li2S—SiS2, Li2S—P2S5, Li2S—GeS2, Li10GeP2S12) and/or sulfide-based lithium argyrodites with formula Li6PS5X (X=Cl, Br) like Li6PS5Cl). Furthermore, the solid electrolyte layer can include a polymer electrolyte material (e.g., a hybrid or pseudo-solid state electrolyte), for example, polyacrylonitrile (PAN), polyethylene oxide (PEO), polymethyl-methacrylate (PMMA), and polyvinylidene fluoride (PVDF), among others.
The battery cell 120 can be included in battery modules 115 or battery packs 110 to power components of the electric vehicle 105. The battery cell housing 230 can be disposed in the battery module 115, the battery pack 110, or a battery array installed in the electric vehicle 105. The housing 230 can be of any shape, such as cylindrical with a circular (e.g., as depicted in
The housing 230 of the battery cell 120 can include one or more materials with various electrical conductivity or thermal conductivity, or any combination thereof. The electrically conductive and thermally conductive material for the housing 230 of the battery cell 120 can include a metallic material, such as aluminum, an aluminum alloy with copper, silicon, tin, magnesium, manganese, or zinc (e.g., aluminum 1000, 4000, or 5000 series), iron, an iron-carbon alloy (e.g., steel), silver, nickel, copper, and a copper alloy, among others. The electrically insulative and thermally conductive material for the housing 230 of the battery cell 120 can include a ceramic material (e.g., silicon nitride, silicon carbide, titanium carbide, zirconium dioxide, beryllium oxide, and among others) and a thermoplastic material (e.g., polyethylene, polypropylene, polystyrene, polyvinyl chloride, or nylon), among others. In examples where the housing 230 of the battery cell 120 is prismatic (e.g., as depicted in
The battery cell 120 can include at least one anode layer 245, which can be disposed within the cavity 250 defined by the housing 230. The anode layer 245 can include a first redox potential. The anode layer 245 can receive electrical current into the battery cell 120 and output electrons during the operation of the battery cell 120 (e.g., charging or discharging of the battery cell 120). The anode layer 245 can include an active substance. The active substance can include, for example, an activated carbon or a material infused with conductive materials (e.g., artificial or natural graphite, or blended), lithium titanate (Li4Ti5O12), or a silicon-based material (e.g., silicon metal, oxide, carbide, pre-lithiated), or other lithium alloy anodes (Li—Mg, Li—Al, Li—Ag alloy etc.) or composite anodes consisting of lithium and carbon, silicon and carbon or other compounds. The active substance can include graphitic carbon (e.g., ordered or disordered carbon with sp2 hybridization), Li metal anode, or a silicon-based carbon composite anode, or other lithium alloy anodes (Li—Mg, Li—Al, Li—Ag alloy etc.) or composite anodes consisting of lithium and carbon, silicon and carbon or other compounds. In some examples, an anode material can be formed within a current collector material. For example, an electrode can include a current collector (e.g., a copper foil) with an in situ-formed anode (e.g., Li metal) on a surface of the current collector facing the separator or solid-state electrolyte. In such examples, the assembled cell does not comprise an anode active material in an uncharged state.
The battery cell 120 can include at least one cathode layer 255 (e.g., a composite cathode layer compound cathode layer, a compound cathode, a composite cathode, or a cathode). The cathode layer 255 can include a second redox potential that can be different than the first redox potential of the anode layer 245. The cathode layer 255 can be disposed within the cavity 250. The cathode layer 255 can output electrical current out from the battery cell 120 and can receive electrons during the discharging of the battery cell 120. The cathode layer 255 can also receive lithium ions during the discharging of the battery cell 120. Conversely, the cathode layer 255 can receive electrical current into the battery cell 120 and can output electrons during the charging of the battery cell 120. The cathode layer 255 can release lithium ions during the charging of the battery cell 120.
The battery cell 120 can include a layer 260 disposed within the cavity 250. The layer 260 can include a solid electrolyte layer. The layer 260 can include a separator wetted by a liquid electrolyte. The layer 260 can include a polymeric material. The layer 260 can include a polymer separator. The layer 260 can be arranged between the anode layer 245 and the cathode layer 255 to separate the anode layer 245 and the cathode layer 255. The polymer separator can physically separate the anode and cathode from a cell short circuit. A separator can be wetted with a liquid electrolyte. The liquid electrolyte can be diffused into the anode layer 245. The liquid electrolyte can be diffused into the cathode layer 255. In the case of a solid electrolyte, the layer 260 can help transfer ions (e.g., Li+ ions) between the anode layer 245 and the cathode layer 255. The layer 260 can transfer Li+ cations from the anode layer 245 to the cathode layer 255 during the discharge operation of the battery cell 120. In the case of a solid electrolyte, the layer 260 can transfer lithium ions from the cathode layer 255 to the anode layer 245 during the charge operation of the battery cell 120. When wetted by a liquid electrolyte, ions (e.g., Li+ ions) can diffuse through the layer 260 (e.g., polymeric separator layer) between the anode layer 245 and the cathode layer 255. The Li+ cations can diffuse through the layer 260 from the anode layer 245 to the cathode layer 255 during the discharge operation of the battery cell 120. The lithium ions can diffuse through the layer 260 from the cathode layer 255 to the anode layer 245 during the charge operation of the battery cell 120.
The redox potential of layers (e.g., the first redox potential of the anode layer 245 or the second redox potential of the cathode layer 255) can vary based on a chemistry of the respective layer or a chemistry of the battery cell 120. For example, lithium-ion batteries can include an LFP (lithium iron phosphate) chemistry, an LMFP (lithium manganese iron phosphate) chemistry, an NMC (Nickel Manganese Cobalt) chemistry, an NCA (Nickel Cobalt Aluminum) chemistry, an OLO (Over Lithiated Oxide) chemistry, or an LCO (lithium cobalt oxide) chemistry for a cathode layer (e.g., the cathode layer 255). Lithium-ion batteries can include a graphite chemistry, a silicon-graphite chemistry, or a lithium metal chemistry for the anode layer (e.g., the anode layer 245).
For example, for a cathode layer (e.g., for cathode layer 255), lithium-ion batteries can include an olivine phosphate (LiMPO4, M=Fe and/or Co and/or Mn and/or Ni)) chemistry, LISICON or NASICON Phosphates (Li3M2(PO4)3 and LiMPO4Ox, M=Ti, V, Mn, Cr, and Zr), for example lithium iron phosphate (LFP), lithium iron manganese phosphate (LMFP), layered oxides (LiMO2, M=Ni and/or Co and/or Mn and/or Fe and/or Al and/or Mg), NMC (Nickel Manganese Cobalt) chemistry, an NCA (Nickel Cobalt Aluminum) chemistry, or an LCO (lithium cobalt oxide) chemistry, as well as lithium rich layer oxides (Li1+xM1-xO2) (Ni, and/or Mn, and/or Co), (OLO or LMR), spinel (LiMn2O4) and high voltage spinels (LiMn1.5Ni0.5O4), disordered rock salt, fluorophosphates such as Li2FePO4F (M=Fe, Co, Ni) and fluorosulfates such as LiMSO4F (M=Co, Ni, Mn). For an anode layer (e.g., for anode layer 245), lithium-ion batteries can include a graphite chemistry, a silicon-graphite chemistry, or a lithium metal chemistry. For example, a cathode layer having an LFP chemistry can have a redox potential of 3.4 V vs. Li/Li+, while an anode layer having a graphite chemistry can have a 0.2 V vs. Li/Li+ redox potential.
Electrode layers can include anode active material or cathode active material, commonly in addition to a conductive carbon material, a binder, or other additives as a coating on a current collector (metal foil). The chemical composition of the electrode layers can affect the redox potential of the electrode layers. For example, cathode layers (e.g., the cathode layer 255) can include medium to high-nickel content (50 to 80%, or equal to 80% Ni) lithium transition metal oxide, such as a particulate lithium nickel manganese cobalt oxide (“LiNMC”), a lithium nickel cobalt aluminum oxide (“LiNCA”), a lithium nickel manganese cobalt aluminum oxide (“LiNMCA”), or lithium metal phosphates like lithium iron phosphate (“LFP”) and lithium manganese iron phosphate (“LMFP”). Anode layers (e.g., the anode layer 245) can include conductive carbon materials such as graphite, carbon black, carbon nanotubes, and the like. Anode layers can include Super P carbon black material, Ketjen Black, Acetylene Black, SWCNT, MWCNT, graphite, carbon nanofiber, or graphene, for example.
Electrode layers can also include chemical binding materials (e.g., binders). Binders can include polymeric materials such as polyvinylidenefluoride (“PVDF”), polyvinylpyrrolidone (“PVP”), styrene-butadiene or styrene-butadiene rubber (“SBR”), polytetrafluoroethylene (“PTFE”) or carboxymethylcellulose (“CMC”). Binder materials can include agar-agar, alginate, amylose, Arabic gum, carrageenan, caseine, chitosan, cyclodextrines (carbonyl-beta), ethylene propylene diene monomer (EPDM) rubber, gelatine, gellan gum, guar gum, karaya gum, cellulose (natural), pectine, poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT-PSS), polyacrylic acid (PAA), poly(methyl acrylate) (PMA), poly(vinyl alcohol) (PVA), poly(vinyl acetate) (PVAc), polyacrylonitrile (PAN), polyisoprene (PIpr), polyaniline (PANi), polyethylene (PE), polyimide (PI), polystyrene (PS), polyurethane (PU), polyvinyl butyral (PVB), polyvinyl pyrrolidone (PVP), starch, styrene butadiene rubber (SBR), tara gum, tragacanth gum, fluorine acrylate (TRD202A), xanthan gum, or mixtures of any two or more thereof.
Current collector materials (e.g., a current collector foil to which an electrode active material is laminated to form a cathode layer or an anode layer) can include a metal material. For example, current collector materials can include aluminum, copper, nickel, titanium, stainless steel, or carbonaceous materials. The current collector material can be formed as a metal foil. For example, the current collector material can be an aluminum (Al) or copper (Cu) foil. The current collector material can be a metal alloy, made of Al, Cu, Ni, Fe, Ti, or any combination thereof. The current collector material can be a metal foil coated with a carbon material, such as carbon-coated aluminum foil, carbon-coated copper foil, or other carbon-coated foil material.
The layer 260 can include or be made of a liquid electrolyte material. For example, the layer 260 can be or include at least one layer of polymeric material (e.g., polypropylene, polyethylene, or other material) that is wetted (e.g., is saturated with, is soaked with, receives) a liquid electrolyte substance. The liquid electrolyte material can include a lithium salt dissolved in a solvent. The lithium salt for the liquid electrolyte material for the layer 260 can include, for example, lithium tetrafluoroborate (LiBF4), lithium hexafluorophosphate (LiPF6), and lithium perchlorate (LiClO4), among others. The solvent can include, for example, dimethyl carbonate (DMC), ethylene carbonate (EC), and diethyl carbonate (DEC), among others. Liquid electrolyte is not necessarily disposed near the layer 260, but the liquid electrolyte can be filled into the battery cells 120 in many different ways. On the other hand, the layer 260 can include or be made of a solid electrolyte material, such as a ceramic electrolyte material, polymer electrolyte material, or a glassy electrolyte material, or among others, or any combination thereof.
In some implementations, the solid electrolyte film includes at least one layer of a solid electrolyte. Solid electrolyte materials of the solid electrolyte layer can include inorganic solid electrolyte materials (e.g., oxides, sulfides, phosphides, ceramics), solid polymer electrolyte materials, hybrid solid state electrolytes, or any combination thereof. In some implementations, the solid electrolyte layer includes polyanionic or oxide-based electrolyte material (e.g., Lithium Superionic Conductors (LISICONs), Sodium Superionic Conductors (NASICONs), perovskites with formula ABO3 (A=Li, Ca, Sr, La, and B=Al, Ti), garnet-type with formula A3B2(XO4)3 (A=Ca, Sr, Ba and X=Nb, Ta), lithium phosphorous oxy-nitride (LixPOyNz). In some implementations, the solid electrolyte layer can include a glassy, ceramic and/or crystalline sulfide-based electrolyte (e.g., Li3PS4, Li7P3S11, Li2S—P2S5, Li2S—B2S3, SnS—P2S5, Li2S—SiS2, Li2S—P2S5, Li2S—GeS2, Li10GeP2S12) and/or sulfide-based lithium argyrodites with formula Li6PS5X (X=Cl, Br) like Li6PS5Cl). Furthermore, the solid electrolyte layer can include a polymer electrolyte material (e.g., a hybrid or pseudo-solid state electrolyte), for example, polyacrylonitrile (PAN), polyethylene oxide (PEO), polymethyl-methacrylate (PMMA), and polyvinylidene fluoride (PVDF), among others.
In examples where the layer 260 includes a liquid electrolyte material, the layer 260 can include a non-aqueous polar solvent. The non-aqueous polar solvent can include a carbonate such as ethylene carbonate, propylene carbonate, diethyl carbonate, ethyl methyl carbonate, dimethyl carbonate, or a mixture of any two or more thereof. The layer 260 can include at least one additive. The additives can be or include vinylidene carbonate, fluoroethylene carbonate, ethyl propionate, methyl propionate, methyl acetate, ethyl acetate, or a mixture of any two or more thereof. The layer 260 can include a lithium salt material. For example, the lithium salt can be lithium perchlorate, lithium hexafluorophosphate, lithium bis(fluorosulfonyl)imide, lithium bis(trifluorosulfonyl)imide, or a mixture of any two or more thereof. The lithium salt may be present in the layer 260 from greater than 0 M to about 1.5 M. Once disposed to the battery cell 120, liquid electrolyte can be present and touching battery subcomponents present within the battery cell 120. The battery subcomponents can include the cathode, the anode, the separator, the current collector, etc.
The battery cell 120 can include one or more components. The component can include the electrode 305. The electrode 305 can include the anode. The anode can include the anode layer 245. The component can include one or more electrolytes 310. The component can include one or more coatings. The component can include one or more additives. As noted above, dissolved Mn2+ (e.g., manganese ions) from the cathode or cathode side of the battery cell 120 can move (e.g., diffuse) to the anode or anode side of the battery cell 120. The dissolved Mn2+ can form MnF2. For example, Mn2+ can react with HF to form MnF2 and H2. The dissolved Mn2+ can react with HF according to Equation 1:
Mn2++2HF→MnF2↓+H2↑ (1)
Mn2+ can reduce to manganese metal (e.g., metallic manganese, Mn(s), Mn0) at approximately 1.8 V. Thus, the reduction of Mn2+ can form manganese metal. For example, reduction of Mn2+ can lead to deposition of manganese metal at the anode. Such manganese metal deposits on the anode side can lead to cell polarization, loss of battery capacity, and increased impedance. For example, manganese metal may increase polarization of the anode. The reduction of Mn2+ can occur at −1.185 V vs. the standard hydrogen electrode (SHE). The reduction of Mn2+ can occur at 1.8 V vs. Li/Li+. The difference between the Li/Li+ potential and SHE is −3.05 V.
The technical solutions of the present disclosure can prevent, reduce, or suppress such manganese metal formation. For example, a technical solution described herein relates to the use of a Mn2+ scavenging species. The Mn2+ scavenging species may be a binary metal fluoride species (MxFy). In some aspects, the binary metal fluoride Mn2+ scavenging species can form a stable ternary metal fluoride compound that includes (e.g., contains) Mn2+ (M-Mn—F). Table 1 provides a listing of suitable metals for the binary metal fluoride Mn2+ scavenging species, and examples of corresponding stable Mn2+-containing ternary fluoride compounds (M-Mn—F).
As reflected in the table, the stable Mn2+-containing ternary fluoride compounds (M-Mn—F) may have the chemical formula MxMn(O1-yFy)z, where M is a metal element (e.g., metal) different from Mn (such as Li, K, Ba, Ca, Na, La, Y, Mg, Ce, or Al), x≥1, 0≤y≤1, and z≥3. Additionally or alternatively, use of the binary Mn2+ scavenging species (MxFy) may result in the formation of MxMn(O1-yFy)z, e.g., through the formation of one or more intermediates. Specific examples of quaternary species of MxMn(O1-yFy)z include oxyfluorides (which could be represented as Mn-M-F—O), where M is a metal different from Mn, such as K, Na, or Ba. In MxMn(O1-yFy)z, x≥1, 0≤y≤1, and z≥3. For example, y can be less than 0.2. The oxyflourides may be formed when reacting with O2− and O− radicals that may be present within the battery cell 120, during electrochemical decomposition. In another embodiment, oxygen impurities may already be present from the starting MxFy precursors. Since the common oxidation state of F is −1 and O is −2, the metal transition oxidation state can be affected upon anion substitutions.
Thus, battery cell 120 can include a binary metal fluoride Mn2+ scavenging species (MxFy) disposed in a component, where M is a metal different from Mn (e.g., a metal cation different from a Mn cation). M can be selected from Li, K, Ba, Ca, Na, La, Y, Mg, Ce, and Al. In some aspects, M is selected from K, Ba and Na (e.g., K+, Ba2+, or Na+). In the formula MxFy, 1≤x≤3 and 1≤y≤3. For example, in some implementations of MxFy, M is K, x=1, and y=1 (KF), or M is Ba, x=1, and y=2 (BaF2), or M is Na, x=1, and y=1 (NaF). Thus, battery cell 120 can include one or more of KF, BaF2, and NaF.
The binary Mn2+ scavenging metal fluoride species MxFy can be disposed in the electrolyte 310. In such implementations, MxFy can be disposed in the electrolyte 310 as an additive salt. For example, one or more of KF, BaF2, and NaF can be dissolved in the electrolyte 310 as an additive salt. In some aspects the electrolyte 310 includes less than 5 wt % of MxFy. In some embodiments, the electrolyte 310 can include MxFy, such as in a range of 0.1 wt % to 5 wt %. For example, the electrolyte 310 can include 0.1 wt % of MxFy, 0.2 wt % of MxFy, 0.3 wt % of MxFy, 0.4 wt % of MxFy, 0.5 wt % of MxFy, 0.6 wt % of MxFy, 0.7 wt % of MxFy, 0.8 wt % of MxFy, 0.9 wt % of MxFy, 1.0 wt % of MxFy, 1.1 wt % of MxFy, 1.2 wt % of MxFy, 1.3 wt % of MxFy, 1.4 wt % of MxFy, 1.5 wt % of MxFy, 1.6 wt % of MxFy, 1.7 wt % of MxFy, 1.8 wt % of MxFy, 1.9 wt % of MxFy, 2.0 wt % of MxFy, 2.5 wt % of MxFy, 3 wt % of MxFy, 3.5 wt % of MxFy, 4 wt % of MxFy, 4.5 wt % of MxFy or 5 wt % of MxFy, or any values in between.
Additionally or alternatively, the binary Mn2+ scavenging metal fluoride species MxFy can be disposed in or on the anode. For example, MxFy (such as one or more of KF, BaF2, or NaF) can be disposed on the anode in a coating (e.g., an anode coating). In such implementations, the coating can include less than 5 wt % of MxFy. For example, the coating can include less than 5 wt % of MxFy, less than 4 wt % of MxFy, less than 3 wt % of MxFy, less than 2 wt % of MxFy, or less than 1 wt % of MxFy. For example, the coating can include 0.5 wt % of MxFy, 1 wt % of MxFy, 1.5 wt % of MxFy, 2 wt % of MxFy, 2.5 wt % of MxFy, 3 wt % of MxFy, 3.5 wt % of MxFy, 4 wt % of MxFy, or 4.5 wt % of MxFy. In some embodiments, the coating can include MxFy such as in a range of 0.1 wt % to 5 wt %. For example, the coating can include 0.1 wt % of MxFy, 0.2 wt % of MxFy, 0.3 wt % of MxFy, 0.4 wt % of MxFy, 0.5 wt % of MxFy, 0.6 wt % of MxFy, 0.7 wt % of MxFy, 0.8 wt % of MxFy, 0.9 wt % of MxFy, 1.0 wt % of MxFy, 1.1 wt % of MxFy, 1.2 wt % of MxFy, 1.3 wt % of MxFy, 1.4 wt % of MxFy, 1.5 wt % of MxFy, 1.6 wt % of MxFy, 1.7 wt % of MxFy, 1.8 wt % of MxFy, 1.9 wt % of MxFy, 2.0 wt % of MxFy, 2.5 wt % of MxFy, 3 wt % of MxFy, 3.5 wt % of MxFy, 4 wt % of MxFy, 4.5 wt % of MxFy or 5 wt % of MxFy, or any values in between.
Additionally or alternatively, MxFy (such as one or more of KF, BaF2, or NaF) can be incorporated in the anode material. For example, MxFy can be a component of a slurry mix used to prepare the anode. In such implementations, the slurry mix can include less than 5 wt % of MxFy. For example, the slurry mix can include less than 5 wt % of MxFy, less than 4 wt % of MxFy, less than 3 wt % of MxFy, less than 2 wt % of MxFy, or less than 1 wt % of MxFy. For example, the coating can include 0.5 wt % of MxFy, 1 wt % of MxFy, 1.5 wt % of MxFy, 2 wt % of MxFy, 2.5 wt % of MxFy, 3 wt % of MxFy, 3.5 wt % of MxFy, 4 wt % of MxFy, or 4.5 wt % of MxFy. In some embodiments, the slurry mix can include MxFy such as in a range of 0.1 wt % to 5 wt %. For example, the slurry mix can include 0.1 wt % of MxFy, 0.2 wt % of MxFy, 0.3 wt % of MxFy, 0.4 wt % of MxFy, 0.5 wt % of MxFy, 0.6 wt % of MxFy, 0.7 wt % of MxFy, 0.8 wt % of MxFy, 0.9 wt % of MxFy, 1.0 wt % of MxFy, 1.1 wt % of MxFy, 1.2 wt % of MxFy, 1.3 wt % of MxFy, 1.4 wt % of MxFy, 1.5 wt % of MxFy, 1.6 wt % of MxFy, 1.7 wt % of MxFy, 1.8 wt % of MxFy, 1.9 wt % of MxFy, 2.0 wt % of MxFy, 2.5 wt % of MxFy, 3 wt % of MxFy, 3.5 wt % of MxFy, 4 wt % of MxFy, 4.5 wt % of MxFy or 5 wt % of MxFy, or any values in between. In some embodiments, MxFy can be coated or blended with the anode active material for the slurry preparation of the cell electrode. MxFy can be coated or deposited physically or chemically on the anode electrode. Additional MxFy may be formed during electrochemical activation, cell formation, and/or cell cycling.
Additionally or alternatively, an anode material comprising MxFy can be prepared during battery electrode preparation by physical addition to the slurry materials. Another example includes electrode post-treatment with target metal precursor with F2 gas treatment or chemical treatment. Within the electrochemical cell, cell formation by providing additional MxFy in an electrolyte can further decompose to form a solid electrolyte interphase (SEI) during electrochemical activation, formation, or cycling of the battery cell. The variation in the voltage cutoff, voltage pulse, C-rate with different current, and/or state-of-charge (SOC) can also impact the SEI formation. The 1st cycle formation of the battery cell 120 can include performing an initial charge and/or discharge operation on the battery cell 120.
As noted above, in some implementations, the binary Mn2+ scavenging metal fluoride species MxFy can react with MnF2 to form a stable ternary Mn2+-containing metal fluoride species (Mn-M-F) as described above, or in some embodiments, oxyfluoride species (e.g., MxMn(O1-yFy)z). For example, KF can react with MnF2 to form K2MnF4; KF can react with MnF2 to form KMnF3; BaF2 can react with MnF2 to form BaMnF4; NaF can react with MnF2 to form NaMnF3, etc. Additionally or alternatively, as noted above, use of the binary Mn2+ scavenging species (MxFy) in the presence of a reactive oxygen species (e.g., which may be present as an impurity or dopant or an electrochemical reduction of O2 gas into O2−/O−) may result in the formation of MxMn(O1-yFy)z, (including oxyfluorides), e.g., through the formation of one or more electrolyte decomposed intermediates that contain oxygen species.
The battery cell 120 can include solid electrolyte interphase 505. The solid electrolyte interphase 505 can be on (e.g., disposed on) the anode active material. As described above, the anode active material can include a binary Mn2+ scavenging metal fluoride species MxFy as described herein, in addition to or as an alternative to a binary Mn2+ scavenging metal fluoride species MxFy being present in the electrolyte. As also described above, the solid electrolyte interphase 505 can include a ternary metal fluoride species (Mn-M-F) or metal oxyfluorides (MxMn(O1-yFy)z). For example, the solid electrolyte interface can include one or more of K2MnF4, KMnF3, BaMnF4, and NaMnF3. The solid electrolyte interface can be one or more of oxyfluoride compounds (O1-yFy) of K2MnF4, KMnF3, BaMnF4, and NaMnF3, including combinations of any two or more thereof.
Thus, in some aspects, the solid electrolyte interphase 505 can include MxMn(O1-yFy)z, where M is a metal different from Mn, such as K, Na, or Ba and x≥1, y=1, and z≥3. Specific examples of ternary species of MxMn(O1-yFy)z include where M is K, x=2, y=1, and z=4; where M is K, x=1, y=1, and z=3; where M is Ba, x=1, y=1, and z=4, and where M is Na, x=1, y=1, and z=3. Specific examples of quaternary species of MxMn(O1-yFy)z include oxyfluorides (which could be represented as Mn-M-F—O), where M is a metal different from Mn, such as K, Na, or Ba. In MxMn(O1-yFy)z, x≥1, 0≤y≤1, and z≥3. For example, y=0.5.
As described above, in some implementations, the binary Mn2+ scavenging metal fluoride species MxFy can react with MnF2 to form a stable ternary Mn2+-containing metal fluoride species (Mn-M-F) as described herein, or metal oxyfluoride species: e.g., MxMn(O1-yFy)z. In such implementations, an amount of the stable ternary Mn2+-containing metal fluoride species (Mn-M-F) in the solid electrolyte interphase 505 can be greater than an amount of such species present in a solid electrolyte interphase of a battery cell that is not provided with a binary Mn2+ scavenging metal fluoride species MxFy. That is, the amount of ternary Mn2+-containing metal fluoride species (Mn-M-F, e.g., MxMn(O1-yFy)z) in a solid electrolyte interphase of a battery cell without MxFy can be less than the amount in a solid electrolyte interphase 505 as described herein. As described above, the binary Mn2+ scavenging metal fluoride species MxFy can be incorporated into the solid electrolyte interphase 505 on the anode during formation of the battery cell 120.
Additionally or alternatively, the ternary Mn2+-containing metal fluoride species (Mn-M-F) is represented as Mx1Mn(O1-yFy)z, where M1 is a metal different from Mn, such as K, Na, or Ba, and the anode active material may includes Ma2Fb as a binary Mn2+ scavenging metal fluoride species, where M2 is a metal different from Mn, such as one or more selected from Li, K, Ba, Ca, Na, La, Y, Mg, Ce, and Al. In the formula Ma2Fb, 1≤a≤3 and 1≤b≤3.
Having now described some illustrative implementations, it is apparent that the foregoing is illustrative and not limiting, having been presented by way of example. In particular, although many of the examples presented herein involve specific combinations of method acts or system elements, those acts and those elements may be combined in other ways to accomplish the same objectives. Acts, elements and features discussed in connection with one implementation are not intended to be excluded from a similar role in other implementations or implementations.
The phraseology and terminology used herein is for the purpose of description and should not be regarded as limiting. The use of “including” “comprising” “having” “containing” “involving” “characterized by” “characterized in that” and variations thereof herein, is meant to encompass the items listed thereafter, equivalents thereof, and additional items, as well as alternate implementations consisting of the items listed thereafter exclusively. In one implementation, the systems and methods described herein consist of one, each combination of more than one, or all of the described elements, acts, or components.
Any references to implementations or elements or acts of the systems and methods herein referred to in the singular may also embrace implementations including a plurality of these elements, and any references in plural to any implementation or element or act herein may also embrace implementations including only a single element. References in the singular or plural form are not intended to limit the presently disclosed systems or methods, their components, acts, or elements to single or plural configurations. References to any act or element being based on any information, act or element may include implementations where the act or element is based at least in part on any information, act, or element.
Any implementation disclosed herein may be combined with any other implementation or embodiment, and references to “an implementation,” “some implementations,” “one implementation” or the like are not necessarily mutually exclusive and are intended to indicate that a particular feature, structure, or characteristic described in connection with the implementation may be included in at least one implementation or embodiment. Such terms as used herein are not necessarily all referring to the same implementation. Any implementation may be combined with any other implementation, inclusively or exclusively, in any manner consistent with the aspects and implementations disclosed herein.
References to “or” may be construed as inclusive so that any terms described using “or” may indicate any of a single, more than one, and all of the described terms. References to at least one of a conjunctive list of terms may be construed as an inclusive OR to indicate any of a single, more than one, and all of the described terms. For example, a reference to “at least one of ‘A’ and ‘B’” can include only ‘A’, only ‘B’, as well as both ‘A’ and ‘B’. Such references used in conjunction with “comprising” or other open terminology can include additional items.
Where technical features in the drawings, detailed description or any claim are followed by reference signs, the reference signs have been included to increase the intelligibility of the drawings, detailed description, and claims. Accordingly, neither the reference signs nor their absence have any limiting effect on the scope of any claim elements.
Modifications of described elements and acts such as variations in sizes, dimensions, structures, shapes and proportions of the various elements, values of parameters, mounting arrangements, use of materials, colors, orientations can occur without materially departing from the teachings and advantages of the subject matter disclosed herein. For example, elements shown as integrally formed can be constructed of multiple parts or elements, the position of elements can be reversed or otherwise varied, and the nature or number of discrete elements or positions can be altered or varied. Other substitutions, modifications, changes and omissions can also be made in the design, operating conditions and arrangement of the disclosed elements and operations without departing from the scope of the present disclosure.
For example, descriptions of positive and negative electrical characteristics may be reversed. Elements described as negative elements can instead be configured as positive elements and elements described as positive elements can instead by configured as negative elements. For example, elements described as having first polarity can instead have a second polarity, and elements described as having a second polarity can instead have a first polarity. Further relative parallel, perpendicular, vertical or other positioning or orientation descriptions include variations within +/−10% or +/−10 degrees of pure vertical, parallel or perpendicular positioning. References to “approximately,” “substantially” or other terms of degree include variations of +/−10% from the given measurement, unit, or range unless explicitly indicated otherwise. Coupled elements can be electrically, mechanically, or physically coupled with one another directly or with intervening elements. Scope of the systems and methods described herein is thus indicated by the appended claims, rather than the foregoing description, and changes that come within the meaning and range of equivalency of the claims are embraced therein.
