WO2023075776A1 - Batterie à électrolyte solide, structure d'électrolyte céramique et procédés de fabrication - Google Patents

Batterie à électrolyte solide, structure d'électrolyte céramique et procédés de fabrication Download PDF

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Publication number
WO2023075776A1
WO2023075776A1 PCT/US2021/057043 US2021057043W WO2023075776A1 WO 2023075776 A1 WO2023075776 A1 WO 2023075776A1 US 2021057043 W US2021057043 W US 2021057043W WO 2023075776 A1 WO2023075776 A1 WO 2023075776A1
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Prior art keywords
electrolyte structure
porous
solid state
anode
porous electrolyte
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PCT/US2021/057043
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English (en)
Inventor
Anil Raj Duggal
Hongyi Zhou
Hongbo Cao
Oltea Puica Siclovan
Kevin Henry Janora
Holly Ann Comanzo
Jie Liu
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General Electric Company
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Priority to PCT/US2021/057043 priority Critical patent/WO2023075776A1/fr
Publication of WO2023075776A1 publication Critical patent/WO2023075776A1/fr

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • 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
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H01M2300/0071—Oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • 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
    • H01M2300/008—Halides
    • 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

Definitions

  • the field of the disclosure relates to solid state batteries and more particularly, to solid state batteries with ceramic electrolyte structures.
  • Rechargeable lithium ion batteries have a high energy density and are a good energy storage system for a wide range of applications.
  • lithium ion batteries have a flammable liquid electrolyte, which can cause the battery to ignite or explode if there is leakage of the electrolyte.
  • Lithium metal batteries have a higher theoretical capacity than conventional lithium ion batteries with a graphite-based anode; however, as a lithium metal anode is not chemically compatible with most liquid electrolytes, a solid state electrolyte is used.
  • Solid state electrolytes such as ceramic-based electrolytes
  • SSEs are a desirable alternative for use in a lithium metal battery system. They provide greater safety, as the electrolyte is a non-flammable solid and will not ignite, and have the potential to provide high energy density at a lower cost.
  • a typical solid state battery (SSB) is formed of a thick dense ceramicbased electrolyte.
  • the ceramic-based SSE is manufactured separately and sintered to provide full density or close to full density with no porosity before being added to the battery as an input material.
  • the thickness of the SSE is dictated by the need to maintain structural integrity during the manufacturing process and is generally greater than 100 micrometers. The large thickness of the SSE reduces the energy density of the battery and separate processing of the SSE adds to manufacturing costs.
  • an improved ceramic-based solid state electrolyte and battery with a reduced tendency for dendrites to form at high current density charging is desirable. Further, is an improved solid state battery with increased energy density for optimal performance, and an improved process for making solid state batteries having a ceramicbased solid electrolyte with reduced manufacturing costs are also desirable.
  • the present disclosure overcomes the problems inherent in the art and provides an improved ceramic-based solid electrolyte structure for a solid state battery with increased safety that can reduce metal dendrite formation at high current densities and provide a solid state battery with higher energy density and reduced manufacturing cost.
  • a porous electrolyte structure for a solid state battery has a thickness and an interconnected ceramic matrix with a network of open pores disposed throughout the thickness of the porous electrolyte structure.
  • the porous electrolyte structure includes a porosity of about 20% by volume to about 80% by volume.
  • a solid state battery cell in another aspect, includes a cathode, an anode and a porous electrolyte structure disposed between the cathode and the anode.
  • the porous electrolyte structure having a thickness and an interconnected ceramic matrix with a network of open pores disposed throughout the thickness of the porous electrolyte structure.
  • the porous electrolyte structure includes a porosity of about 20% by volume to about 80% by volume.
  • the method includes forming a porous electrolyte structure having a thickness and an interconnected ceramic matrix with a network of open pores disposed throughout the thickness of the porous electrolyte structure and inserting the porous electrolyte structure between an anode and a cathode.
  • the porous electrolyte structure includes a porosity of about 20% by volume to about 80% by volume.
  • the various aspects of the disclosure provide improved solid state electrolytes and batteries having higher current densities with reduced dendrite formation, high energy density, increased safety and reduced cost.
  • Figure 1A is a schematic drawing of a conventional solid state battery in a charged state.
  • Figure IB is a schematic drawing of a conventional solid state battery in a discharged state.
  • Figure 2 is a schematic drawing of a portion of a conventional solid state battery.
  • Figure 3 is a schematic drawing of a portion of a solid state ceramic battery cell in accordance with an aspect of the disclosure.
  • Figure 4A is a schematic diagram of a solid state battery cell in a charged state in accordance with an aspect of the disclosure.
  • Figure 4B is a schematic diagram of a solid state battery cell in a discharged state in accordance with an aspect of the disclosure.
  • Figure 5 A is a schematic diagram of a solid state battery cell in a charged state in accordance with an aspect of the disclosure.
  • Figure 5B is a schematic diagram of a solid state battery cell in a discharged state in accordance with an aspect of the disclosure.
  • Figure 6A is a schematic diagram of a solid state battery cell prior to initial charge in accordance with an aspect of the disclosure.
  • Figure 6B is a schematic diagram of a solid state battery cell prior to initial charge in accordance with an aspect of the disclosure.
  • Figure 7A is a schematic diagram of a solid state battery cell in a charged state in accordance with an aspect of the disclosure.
  • Figure 7B is a schematic diagram of a solid state battery cell in a discharged state in accordance with an aspect of the disclosure.
  • Figure 8 is a schematic diagram of the solid state battery cell assembly prepared in the Examples.
  • Figure 9 is a graph showing current (A) as a function of cycle time (s) from the testing cycles in Example 1.
  • Figure 10 is a graph showing cell voltage (V) as a function of cycle time (s) from the testing cycles in the Example 1.
  • Figure 11 is a schematic of the high rate heat treatment in Example 2.
  • Figure 12 is a graph showing current density (mA/cm 2 ) as a function of cycle time (hr) from the testing cycles in Example 2.
  • Figure 13 is a graph showing cell voltage (V) as a function of cycle time (hr) from the testing cycles in Example 2.
  • “Optional” or “optionally” means that the subsequently described event or circumstance may or may not occur, or that the subsequently identified material may or may not be present, and that the description includes instances where the event or circumstance occurs or where the material is present, and instances where the event or circumstance does not occur or the material is not present.
  • porosity measurements provided for the electrolyte structure are based on the volume of the porous electrolyte structure.
  • the various aspects of the disclosure provide improved ceramic solid state electrolytes and solid state batteries with ceramic solid state electrolytes having higher current densities with reduced dendrite formation, high energy density, increased safety and reduced cost.
  • a solid state battery cell includes a cathode, an anode and a porous electrolyte structure disposed between the cathode and the anode.
  • the porous electrolyte structure having a thickness and an interconnected ceramic matrix with a network of open pores disposed throughout the thickness of the porous electrolyte structure.
  • the porous electrolyte structure including a porosity of about 20% by volume to about 80% by volume.
  • a solid state battery cell includes an anode or negative electrode, a cathode or positive electrode and a solid electrolyte structure or solid ionic conductor situated between the electrodes for conducting ions between the cathode and anode.
  • the solid electrolyte structure is a ceramic material and is configured to move ions while resisting the flow of electrons, which allows electrons to move outside the battery.
  • FIG. 1A and IB show a conventional battery cell 100 having a cathode 110 with a thickness of about 50 micrometers and an aluminum current collector 115 having a thickness of about 10 micrometers, an anode 120 having a copper current collector and having a thickness of about 10 micrometers, and a solid ionic conductor or solid electrolyte 130 prepared from a dense ceramic material and having a thickness of about 240 micrometers.
  • Figure 1A depicts the solid state battery cell in a charged state
  • Figure IB depicts the solid state battery cell in a discharged state.
  • FIG. 2 depicts a conventional solid state battery cell 200 where a lithium dendrite 210 has formed at an imperfection 220 on an interface 230 between a dense ceramic electrolyte 240 and an anode 250.
  • a porous electrolyte structure for a solid state battery having a thickness and an interconnected ceramic matrix with a network of open pores disposed throughout the thickness of the porous electrolyte structure.
  • the porous electrolyte structure including a porosity of about 20% by volume to about 80% by volume.
  • a solid electrolyte structure or solid ionic conductor is situated between the electrodes for conducting ions between the cathode and anode and is configured to move ions, such as lithium or sodium ions, while resisting the flow of electrons, which allows electrons to move outside the battery.
  • the solid electrolyte structure is porous with an interconnected ceramic matrix and a network of open pores disposed throughout the solid electrolyte.
  • the porous structure includes a plurality of open pores extending from the surface and disposed throughout the thickness of the solid state electrolyte.
  • the ceramic matrix and the open pore network are continuous forming two interpenetrating continua.
  • the pores or void spaces may be uniform in size and shape or irregularly formed.
  • the pores have an average pore diameter from about 50 nm to about 500 pm. In another aspect, the pores have an average pore diameter ranging from about 100 nm to about 500 pm. In another aspect, the pores have an average pore diameter from about 50 nm to about 500 nm.
  • the porous electrolyte structure has a porosity of about 20% by volume to about 80% by volume. In another aspect, the porous electrolyte has a porosity of about 20% by volume to about 70% by volume. In another aspect, the porosity may be about 30% by volume to about 80% by volume and in another aspect, the porosity may be from about 30% by volume to about 70% by volume. In another aspect, the porosity is 30% by volume to about 60% by volume, based on the volume of the porous electrolyte structure. In another aspect, the porosity may be about 50% by volume to about 80% by volume and in another aspect, the porosity may be from about 50% by volume to about 70% by volume.
  • the porosity is from about 50% by volume to about 60% by volume. In one aspect, the electrolyte structure has a porosity of at least 30% by volume. In another aspect, the electrolyte structure has a porosity of at least 50% by volume.
  • the porous electrolyte structure with its open pore network provides the battery cell with empty spaces.
  • the metal ions deposit and are reduced on the anode and stress begins to build from the volume change in the battery cell, the metal can begin to fill the available empty spaces of the pores. This leads to a reduced volume change of the battery as a whole and limits any stress build-up formed at the interface of the anode and electrolyte.
  • the reduction of the stress build-up reduces dendrite formation in the ceramic electrolyte even at high current densities.
  • FIG. 3 illustrates a portion of a solid state battery cell 300 during a charging cycle.
  • the battery cell 300 has a porous electrolyte structure 310 with an interconnected ceramic matrix 315 and a network of open pores 320 extending from the surface and disposed throughout the thickness of the electrolyte structure.
  • the metal 350 can either push the solid-state electrolyte structure 310 away from the anode surface 340 or move into an open pore space 320. This relieves stress build-up at the interface of the anode surface 340 and the electrolyte structure 310 and reduces the chance of dendrite formation.
  • Figure 4A shows the battery in a charged state
  • Figure 4B shows the battery in a discharged state
  • Figures 4A and 4B show a battery cell 400 having a cathode 410 with a thickness of about 50 micrometers and an aluminum current collector 415 having a thickness of about 10 micrometers, an anode 420 having a copper or nickel current collector and having a thickness of about 10 micrometers and a solid ionic conductor or porous electrolyte structure 430 prepared from a porous ceramic material and having a thickness of about 20 micrometers.
  • the porous electrolyte structure 430 has an interconnected ceramic matrix 435 with a network of open pores 440 extending from the surface and disposed throughout the thickness of the electrolyte structure.
  • positive ions such as lithium or sodium ions
  • the thickness of the battery in the discharged state shown in Figure 4B is 90 micrometers; while the thickness of the battery in the charged state remains at about 90 micrometers.
  • the reduced volume change in the battery cell between the charged and discharged states eliminates stress from concentration change and reduces dendrite formation.
  • the porous electrolyte structure includes a ceramic electrolyte material.
  • the ceramic material may be any ceramic material having low electronic conductivity with a high ionic transference number, high ionic conductivity, mechanical strength, temperature stability and which is electrochemically stable with the electrode materials.
  • the ceramic material has an ionic conductivity of above IO' 4 S/cm at room temperature.
  • the ceramic material includes, but is not limited to, NASICON-type (sodium super ionic conductor), garnet-type, perovskite-type, LISICON-type (lithium super ionic conductor-type), LiPON-type (lithium phosphorus oxynitride), lithium nitride-type, sulfide-type, agryrodite-type, anti-perovskite-type or mixtures thereof.
  • the NASICON-type material may include a NASICON-type Li-ion material.
  • the garnet-type material may include a lithium- containing garnet material.
  • the perovskite-type material may include lithium lanthanum titanate (LLTO), lithium strontium tantalum zirconium oxide (LSTZ), lithium strontium tantalum hafnium oxide (LSTH) or lithium strontium niobium zirconium oxide (LSNZ).
  • the sulfide-type material may be lithium phosphorus sulfide (LPS).
  • the NASICON-type Li-ion material has the formula LiM2(PO4)3, where M is Ti or Ge.
  • the NASICON-type Li-ion material may be doped with aluminum or scandium.
  • the lithium-containing garnet material may be lithium lanthanum zirconium oxide (LLZO).
  • the LLZO has the formula Li 7 La 3 Zr 2 O 12 .
  • LLZO may be doped with aluminum, tantalum or gadolinium.
  • LLTO has the formula Li 3-x La 2/3 - x TiO 3 , where 0 ⁇ x ⁇ 2/3.
  • LSTZ has the formula Li 3/8 Sr7/ 16 Ta 3/4 Zr 1/4 O 3 .
  • LSTH has the formula Li 3/8 Sr 7/16 Ta 3/4 Hf 1/4 O 3 .
  • LSNZ has the formula Li 3/8 Sr 7/16 Nb 3/4 Hf 1/4 Zr 1/4 O 3 .
  • LISICON-type material has the formula y- Li3PO4.
  • the ceramic material includes, but is not limited to: LiTi 2 (PO 4 ) 3 ; LiTi 2 (PO 4 ) 3 -0.2Li 3 BO 3 ; Lii.3Alo.3Tii.7(PO 4 ) 3 ; Li 1.3 M 0.3 Ti 1.7 (P0 4 ) 3 , where M is A1 or Sc; 2[Li 1.4 Ti 2 Si 0.4 P 2.6 O 12 ]-AlPO 4 ; 100[Lii.5Cro.5Tii.5(P0 4 ) 3 ]-5SiO 2 ;
  • the solid electrolyte material may include additional materials, such as lithium borate, lithium phosphate, lithium titanium phosphate, lithium tetraborate (Li2B4O?), lithium carbonate (Li2CO3) and eutectic flux materials, such as LiCkKCl, SrCh:LiCl and CaCl 2 :LiCl.
  • additional materials such as lithium borate, lithium phosphate, lithium titanium phosphate, lithium tetraborate (Li2B4O?), lithium carbonate (Li2CO3) and eutectic flux materials, such as LiCkKCl, SrCh:LiCl and CaCl 2 :LiCl.
  • the porous ceramic solid state electrolyte structure may be manufactured with the battery cell allowing the electrolyte structure to be thinner than if it were manufactured separately and required a thicker supporting structure.
  • the porous electrolyte structure has a thickness of 100 micrometers or less.
  • the electrolyte structure has a thickness ranging from about 10 micrometers to about 100 micrometers.
  • the electrolyte structure has a thickness in a range of from about 10 micrometers to about 50 micrometers.
  • the electrolyte structure has a thickness from about 10 micrometers to about 30 micrometers.
  • the electrolyte structure is about 18 micrometers to 20 micrometers thick.
  • the solid state electrolyte structure includes a coating covering the interconnected ceramic matrix forming the open pore network.
  • the coating includes ionically insulating material or lithium-wetting materials. Ionically insulating material helps to ensure that the lithium ions are reduced to metal at the solid state electrolyte interface with the anode or with an anode interface layer (described below), if present. This causes the metal to extrude up from the anode or anode interface layer into the pores rather than to grow out from the sides of the ceramic matrix without filling in the open pore spaces.
  • the ionically insulating material has an ionic conductivity value that is less than 10% of the ionic conductivity of the solid state electrolyte material.
  • the ionically insulating material includes lithium carbonate Q ⁇ CCh).
  • the coating includes lithium- wetting materials, which promote complete filling of reduced lithium metal within pores of the porous electrolyte.
  • a lithium-wetting material includes aluminum oxide (AI2O3).
  • the coating covers the interconnected ceramic matrix of the porous electrolyte structure without closing or filling up the pore spaces. In one aspect, there is no coating between the anode and the solid state electrolyte, which would prevent contact between the metal ions and electrons from the current collector. In one aspect, there is no coating between the cathode and the solid state electrolyte, which would prevent metal ions from transferring between the cathode and the solid state electrolyte. In some embodiments, the interconnected ceramic matrix is partially coated. In some embodiments, the interconnected ceramic matrix is fully coated. In another embodiment, from about 10 percent to about 90 percent of the total extent or thickness of the ceramic matrix is coated.
  • from about 15 percent to about 85 percent of the total extent or thickness of the ceramic matrix is coated. In another embodiment, from about 20 percent to about 80 percent of the total extent or thickness of the ceramic matrix is coated. In another embodiment, from about 25 percent to about 75 percent of the total extent or thickness of the ceramic matrix is coated.
  • the porous solid state electrolyte structure includes a coated section and a non-coated section.
  • the coated section of the electrolyte structure is situated adjacent the anode section or an anode interface layer and adjacent the non-coated section of the electrolyte structure.
  • the coated section is from about 10 percent to about 75 percent of the total extent or thickness of the electrolyte structure.
  • the coated section is from about 15 percent to about 75 percent of the electrolyte structure.
  • the coated section is from about 20 percent to about 75 percent of the electrolyte structure.
  • the coated section is from about 25 percent to about 75 percent of the electrolyte structure.
  • the porous electrolyte structure includes a coated section having a thickness from about 1 micrometer to about 75 micrometers. In another aspect, the electrolyte structure includes a coated section having a thickness from about 1 micrometer to about 40 micrometers. In another aspect, the electrolyte structure includes a coated section having a thickness from about 1 micrometer to about 20 micrometers. In another aspect, the electrolyte structure includes a coated section having a thickness from about 2 micrometers to about 15 micrometers thick.
  • the coating has a thickness of up to about 1 pm. In another aspect, the coating has a thickness of about 50 nm to about 1 pm. In one aspect, the coating is lithium carbonate.
  • FIG. 5A shows the battery in a charged state
  • Figure 5B shows the battery in a discharged state
  • Figures 5A and 5B show a battery cell 500 having a cathode 510 with an aluminum current collector 515, an anode 520 having a copper or nickel current collector and a solid ionic conductor or porous electrolyte structure 530 prepared from a porous ceramic material.
  • the porous electrolyte structure 530 has an interconnected ceramic matrix 545 with a network of open pores 540 extending from the surface and disposed throughout the thickness of the electrolyte structure 530.
  • a coating 535 such as an ionically insulating coating or a lithium-wetting coating, covers the ceramic matrix 545.
  • ions such as lithium or sodium ions, move toward the anode and are reduced and deposit as metal 550 on the anode 520 and into the open pore spaces 540 in the porous electrolyte structure 530.
  • the solid state battery cell includes a cathode or positive electrode including a metal or metal alloy current collector and a cathode metal ionconducting material, such as a cathode lithium ion-conducting material or cathode sodium ion-conducting material. Wires can be attached to the current collector to provide a path for electron flow from an external circuit.
  • the current collector is a conducting metal or metal alloy.
  • the current collector is aluminum.
  • the current collector has a thickness of about 10 micrometers to about 20 micrometers.
  • the cathode material includes, but is not limited to LiTiS2; LiCoCh; LiNiCh; LiMnCh; LiNio.33Mno.33Coo.33O2; LiNi0.8Co0.15Al0.05O2, Li2MnO3; LiMn 2 O 4 ; LiCo 2 O 4 ; LiFePO 4 ; LiMnPO 4 ; LiCoPO 4 ; LiFeSO 4 F; LiVPO 4 F; FeF 2 ; FeF 3 ; CoF 2 ; CUF 2 ; NiF 2 ; BiF 3 ; FeCh; FeCl 2 ; C0CI2; NiCl 2 ; CuCl 2 ; AgCl; LiCl; S; Li 2 S; Se; Li2Se; Te; I; Lil, and combinations thereof.
  • the cathode is a lithium iron phosphate infiltrated with liquid electrolyte.
  • the cathode contains additives, such as carbon to increase electrical conductivity.
  • the cathode contains binder materials.
  • the cathode is coated on the current collector.
  • the cathode material has a thickness of about 50 micrometers to about 100 micrometers. In one aspect, the cathode may have a thickness of about 60 micrometers to about 120 micrometers.
  • the solid state battery cell includes an anode or negative electrode including a metal or metal alloy current collector.
  • the anode may include a current collector coated with a metal, such as lithium metal or sodium metal. Wires can be attached to the current collector to provide a path for electron flow from an external circuit.
  • the current collector is a conducting metal or metal alloy.
  • the current collector is copper or nickel. In one aspect, the current collector has a thickness of about 10 micrometers.
  • the solid state battery cell includes a solid state electrolyte interface layer between the electrode and the porous electrolyte structure.
  • a solid state electrolyte interface layer disposed between an electrode and electrolyte helps to improve the contact between the electrode (cathode or anode) and the porous electrolyte structure.
  • the battery cell includes a cathode interface layer between the cathode and the porous electrolyte structure.
  • the battery cell includes an anode interface layer between the anode and the porous electrolyte structure.
  • FIGS. 5A and 5B discussed previously show a solid state battery cell with a cathode interface layer 570 between the cathode 510 and the porous electrolyte structure 530 and an anode interface layer 580 between the anode 520 and the porous electrolyte structure 530.
  • the interface layers can improve the contact between the SSE and the current collector. They can be ionically conductive, electrically conductive or both. They may be prepared from any conventional material used for making interface layers.
  • the interface layers may be solid polymer electrolyte, such as polyethylene oxide with bis(trifluoromethylsulfonyl)amine lithium salt or a combination of other lithium salt compounds.
  • the interface layer may be a membrane.
  • the interface layer may be a lithophilic coating, such as aluminum oxide.
  • the interface layer may be formed from a polymer gel electrolyte.
  • the interface layer may be applied by atomic layer deposition.
  • the SSE may interpenetrate into the interface layers.
  • the interface layer may have a thickness of about 10 nm to about 170 micrometers. In another aspect, the interface layer may be a coating having a thickness from about 10 nm to about 100 nm. In another aspect, the interface layer has a thickness from about 150 micrometers to about 170 micrometers.
  • additional metal such as sodium or lithium may be added to the solid state battery cell during manufacture and prior to operation to provide the battery cell with more metal than can be provided by the cathode material.
  • additional metal can be placed between the anode current collector and the porous electrolyte structure.
  • the additional metal can be placed between the anode current collector and an anode interface layer. In these aspects, during battery cycling, erosion of the additional metal can also occur moving the metal into the porous electrolyte structure.
  • the additional metal can be placed between the cathode and the porous electrolyte structure. In another aspect, the additional metal can be placed between the cathode and a cathode interface layer. In these aspects, during battery cycling, the additional metal can also move into the open pores of the porous electrolyte structure or to a position between the porous electrolyte structure and the anode or into either position.
  • FIGS. 6A and 6B show a battery cell 600 having a cathode 610 and an aluminum current collector 615, a cathode interface layer 670, an anode 620 having a copper or nickel current collector, an anode interface layer 680 and a solid ionic conductor or porous electrolyte structure 630 prepared from a porous ceramic material.
  • the porous electrolyte structure 630 has an interconnected ceramic matrix 645 with a network of open pores 640 extending from the surface and disposed throughout the thickness of the electrolyte structure 630.
  • a coating 635 such as an ionically insulating coating or a lithium- weting coating covers the ceramic matrix 645.
  • additional metal 690 such as lithium or sodium, is positioned in the batery cell between the anode 620 and the anode interface layer 680.
  • additional metal 690 is positioned in the batery cell between the cathode interface layer 670 and the porous electrolyte structure 630.
  • a method for producing a solid state batery cell includes forming a porous electrolyte structure having a thickness and an interconnected ceramic matrix with a network of open pores disposed throughout the thickness of the porous electrolyte structure and inserting the porous electrolyte structure between an anode and a cathode.
  • the porous electrolyte structure includes a porosity of about 20% by volume to about 80% by volume, based on the volume of the porous electrolyte structure.
  • the porous electrolyte may be manufactured together with the solid state batery cell, rather than in a separate process. Manufacturing the porous electrolyte with the solid state batery cell allows the porous electrolyte to be thinner and reduces the manufacturing costs of the batery cell. In some embodiments, battery performance is enhanced if the porous electrolyte is heated during battery fabrication. While not being bound by theory, this improvement can be due to the volatilization of impurities and/or the enhancement of particle connections.
  • the electrolyte material such as ceramic electrolyte material
  • the anode such as a copper or nickel foil.
  • the electrolyte material is coated on the anode or anode interface layer.
  • the electrolyte material is applied to the anode as a slurry with a solvent.
  • the electrolyte material is heat treated.
  • the electrolyte material is heat treated from about 850°C to about 1200°C.
  • the electrolyte material is heat treated for a time and temperature effective to cure the electrolyte material.
  • the electrolyte material may be heat treated at 850°C for about 2 hours.
  • the electrolyte material may be cured with a high-rate heat treatment.
  • a high-rate heat treatment can be advantageous in reducing cost by reducing manufacturing time.
  • a high-rate heat treatment can also be advantageous in locking in a desired porous electrolyte structure by minimizing the time during which components of the porous electrolyte can deform or move during a high temperature fabrication step.
  • the electrolyte material such as ceramic electrolyte material, is heated with resistance heating by supplying a current through a resistance heating element.
  • the electrolyte material is heat treated by contacting or in close proximity to a resistance heating element, such as an alumina-coated tungsten strip. Resistance heating may include one or more resistive heating elements.
  • the electrolyte material is heated and cured within about 10 seconds to about 5 minutes. In another embodiment, the electrolyte material may be heated from about 15 seconds to about 5 minutes. In another embodiment, the electrolyte material may be heated from about 20 seconds to about 3 minutes. In another embodiment, the electrolyte material may be heated from about 30 seconds to about 2 minutes. In another embodiment, the electrolyte material may be heated from about 30 seconds to about 1 minute.
  • the high-rate heat treatment is at a temperature greater than 850°C. In another embodiment, the temperature for the high-rate heat treatment is from about 1000°C to about 3000°C. In another embodiment, the temperature for the high-rate heat treatment is from about 1000°C to about 2000°C. In one embodiment, the electrolyte material may be heated to 1200°C for about 30 seconds.
  • pore sizes and connectivity of the pores may be controlled within the electrolyte structure.
  • pore sizes may be formed in the electrolyte structure by including pore-forming materials or other sacrificial materials in the preparation of the electrolyte structure. For example, pore-forming materials can be added to porous electrolyte precursor coating material.
  • poreforming materials include organic molecules, oligomers, polymers and copolymers, such as, but not limited to cellulose, ethyl cellulose, polystyrene, polycarbonate, polyacrylates, polymethacrylates, such as polymethyl methacrylate (PMMA), polyurethane, poly etherether ketone, poly sulfones, poly (vinyl alcohol), poly(l,2-butylene glycol), polyethyleneglycol, poly(styrene-co-divinylbenezene), and mixtures thereof.
  • the poreforming materials can be incorporated into the electrolyte material in any form or shape, such as, but not limited to dissolved solutions, extruded mixtures, ground mixtures, hot- melt mixtures, particles, and fibers.
  • the pore-forming material may be included in an amount of from about 1 to about 50 weight percent of the electrolyte material.
  • the electrolyte material is heated to a temperature sufficient to volatilize the pore-forming material forming a porous electrolyte structure.
  • the electrolyte material is heated to a temperature in a range from about 500°C to about 800°C.
  • the electrolyte may be heated in a range from about 500°C to about 700°C.
  • the electrolyte material may be heated for a time sufficient to volatize the pore-forming materials. In one embodiment, the electrolyte material is heated from about 1 to about 3 hours.
  • the electrolyte material may be heated for about 1 to about 2 hours. In one embodiment, the electrolyte with pore-forming material may be heated to about 600°C for about 2 hours to volatilize the pore-forming material before the electrolyte material is cured to form a ceramic electrolyte material.
  • the ceramic matrix of the porous electrolyte structure may be coated with an ionically insulating material or a lithium-wetting material in any conventional manner.
  • the ceramic matrix of the porous electrolyte structure is coated with lithium carbonate.
  • the ceramic matrix is coated by infiltrating the porous electrolyte structure with carbon dioxide. The carbon dioxide gas reacts with the ceramic material to form a coating on the ceramic matrix.
  • the coating on the ceramic matrix is up to about 1 pm thick.
  • the coating has a thickness of about 500 nm to about 1 pm.
  • Coating for the electrolyte structure can be formed by flowing carbon dioxide gas through the electrolyte structure.
  • the coating is lithium carbonate.
  • the ceramic matrix of the porous electrolyte structure is coated with a lithium-wetting coating.
  • the lithium-wetting coating may be applied by atomic layer deposition.
  • the lithium-wetting coating on the ceramic matrix has a thickness from about 2 nm to about 100 nm.
  • the coating thickness is from about 5 nm to about 75 nm.
  • the coating thickness is from about 10 nm to about 100 nm.
  • the coating thickness is from about 10 nm to about 50 nm.
  • the coating thickness is from about 25 nm to about 75 nm.
  • the porous electrolyte structure is coated with aluminum oxide and having a coating thickness from about 2 nm to about 100 nm.
  • the solid ceramic electrolyte structure includes a porous portion and a dense portion.
  • the porous portion is disposed between the anode and the dense portion of the solid electrolyte.
  • the porous portion has an interconnected ceramic matrix with a network of pores disposed throughout the porous portion as described above and may be configured to hold anode material within the pores when the battery cell is in a charged state.
  • the dense portion includes a porosity of about 80% by volume to about 100% by volume.
  • the dense portion includes a porosity of about 80% by volume to about 95% by volume.
  • the dense portion includes a porosity of about 80% by volume to about 90% by volume.
  • Figure 7A shows the battery in a charged state
  • Figure 7B shows the battery in a discharged state
  • Figures 7A and 7B show a battery cell 700 having a cathode 710 and an aluminum current collector 715, an anode 720 having a copper or nickel current collector and a solid ceramic electrolyte structure 730 including a porous portion 732 and a dense portion 734.
  • the porous portion 732 has an interconnected ceramic matrix 745 with a network of open pores 740 extending from the surface and disposed throughout the thickness of the porous portion 732.
  • a coating 735 such as an ionically insulating coating or a lithium-wetting coating, covers the ceramic matrix 745.
  • ions such as lithium or sodium ions, move toward the anode and are reduced and deposit as metal 750 on the anode 720 and into the open pore spaces 740 in the porous portion 732.
  • the battery cell may be assembled by applying a cathode to the porous electrolyte, such that the electrolyte is between the cathode and anode and contacts the cathode and anode.
  • additional layers may be included in the battery cell.
  • the battery cell may include a cathode interface layer, which is sandwiched between the cathode and porous electrolyte structure during the battery cell assembly.
  • the battery cell includes an anode interface layer, which is sandwiched between the anode and the porous electrolyte structure during the battery cell assembly.
  • porous electrolyte structure and the battery cell may be made into any suitable shape.
  • Cathode LiFePCL (LFP) coated (83 micrometers thickness) on an Aluminum electrode (20 micrometers thickness) backing from MTI Corp.
  • Anode 5 mil thick copper disks (10 micrometers thickness) were cleaned and etched for 15 -20s in a 20 wt% ammonium persulfate aqueous solution to prepare the anode.
  • Al-doped lithium lanthanum zirconium oxide (Al-LLZO) ceramic nano-powder with a D50 412 nm from Ampcera
  • Slurry A was prepared by dispersing the electrolyte material in ethylene glycol (60 wt% solids loading) to form a homogeneous slurry.
  • Slurry B was prepared by adding 8wt% LisBCL sieved below 25 micrometers and mixing with the Al-LLZO nano-powder before the addition of ethylene glycol. The solids loading of the slurry was lowered to 49-50 wt% to obtain a homogeneous slurry. [0093] Slurry A was coated onto 5 mil thick copper disks (anode material) using a doctor blade with a 5 mil gap. Slurry B was coated onto different 5 mil thick copper disks (anode material) using a doctor blade with a 5 mil gap.
  • the coated copper disks were dried in a vacuum oven (20-25 mm Hg) at 115°C overnight and then pressed at 9 Ton between two highly polished hardened steel plates, using a manual press.
  • the coated Copper disks were heat treated for 2 hours at 850°C in a quartz tube furnace under an Argon atmosphere.
  • the electrolyte thickness is 20 micrometers.
  • the ceramic coated disks were immediately stored in an inert atmosphere in order to prevent surface carbonation.
  • the CR 2032 cells were assembled in an Argon environment by sandwiching the PEG + LiTFSl membrane between the prepared ceramic coated disk and cathode.
  • Total cell thickness ranged from 283 micrometers to 303 micrometers.
  • FIG. 8 shows a solid state battery cell assembly 800 having a cathode 810 and an aluminum current collector 815, a cathode interface layer 870, an anode 820 having a current collector and a solid ionic conductor or porous electrolyte structure 830 prepared from a porous ceramic material.
  • the porous ceramic material is Al-LLZO + Li 3 BO 3 from slurry B.
  • the porous electrolyte structure 830 has an interconnected ceramic matrix 845 with a network of open pores 840 extending from the surface and disposed throughout the thickness of the electrolyte structure 830.
  • Cathode LiFePCL (LFP) coated (83 micrometers thickness) on an Aluminum electrode (20 micrometers thickness) backing from MTI Corp.
  • Anode 5 mil thick Nickel disks having a diameter of 9/16” (about 14.3 mm) were punched and hammer flattened between highly polished stainless steel plates.
  • Al-doped lithium lanthanum zirconium oxide (Al-LLZO) ceramic nano-powder with a D50 412 nm from Ampcera
  • Polymer solution A polymer solution was prepared by dissolving 1.08 grams of ethyl cellulose (Aldrich product No. 46070) in 17 grams of a mixture solvent of terpineol (Aldrich product No. 77663) and 2-(2-Butoxyethoxy)ethyl acetate (BEA) (Aldrich product No. 537535) in a 1-to-1 ratio, which was stirred at 60°C and 800 rpm overnight to obtain a clear solution.
  • An electrolyte material slurry was prepared by adding Li 3 BO 3 sieved below 25 micrometers to the Al-LLZO nano-powder and dry mixing the powder before the addition of the polymer solution. Weight ratio of Al-LLZO:Li3BO3:Polymer solution is 2.88g:0.12g:2.0g. All components of the electrolyte slurry were mixed well to obtain a homogeneous mixture.
  • the freshly prepared electrolyte material slurry was coated onto 5 mil thick nickel disks (anode material) using a doctor blade with an 8 mil gap.
  • the coated nickel disks were dried in a vacuum oven (20-25 mm Hg) at 115 °C overnight. After drying, the coated nickel disks were placed facing up into an alumina tray, which was subsequently loaded into a quartz tube furnace under a nitrogen atmosphere. The temperature of the furnace was ramped up from ambient temperature to 600°C, heated for 2 hours and then cooled down to room temperature. During heat treatment, the pore-forming materials, i.e. ethyl cellulose, and any residual solvent were volatilized and burned off.
  • the coated nickel disks were then subjected to a high-rate heat treatment, as shown in FIG. 11.
  • a nickel disk 1110 coated with electrolyte material 1120 was placed on an alumina-coated tungsten strip 1130 within a well 1140 situated in the center of the strip 1130 and the strip 1130 was resistively heated passing a current 1150 though the alumina-coated tungsten strip 1130 to ⁇ 1200°C for 30 seconds in an argon atmosphere.
  • the ceramic coated disks were stored in an inert atmosphere to prevent surface carbonation.
  • the electrolyte thickness was 20 micrometers.
  • the CR 2032 cells were assembled in an Argon environment by sandwiching the PEO + LiTFSI membrane between the prepared ceramic coated disk and cathode.
  • Total cell thickness ranged from 283 micrometers to 303 micrometers.
  • FIG. 8 shows a solid state battery cell assembly 800 having a cathode 810 and an aluminum current collector 815, a cathode interface layer 870, an anode 820 having a current collector and a solid ionic conductor or porous electrolyte structure 830 prepared from a porous ceramic material.
  • the porous ceramic material is Al-LLZO + Li 3 BO 3 .
  • the porous electrolyte structure 830 has an interconnected ceramic matrix 45 with a network of open pores 840 extending from the surface and disposed throughout the thickness of the electrolyte structure 830.

Abstract

L'invention concerne une structure d'électrolyte poreux pour une batterie à semi-conducteurs. La structure d'électrolyte poreux a une matrice céramique interconnectée avec un réseau de pores ouverts disposés sur toute une épaisseur de la structure d'électrolyte poreux. La structure d'électrolyte poreux comprend une porosité d'environ 20 % en volume à environ 80 % en volume. L'invention concerne également un élément de batterie à semi-conducteurs comprenant la structure d'électrolyte poreux et un procédé de fabrication de l'élément de batterie à semi-conducteurs.
PCT/US2021/057043 2021-10-28 2021-10-28 Batterie à électrolyte solide, structure d'électrolyte céramique et procédés de fabrication WO2023075776A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080102337A1 (en) * 2005-02-28 2008-05-01 The Tokyo Electric Power Company, Incorporated Solid Oxide Type Fuel Battery Cell and Process for Producing the Same
WO2018089430A1 (fr) * 2016-11-08 2018-05-17 Fisker Inc. Batteries li-ion tout solide comprenant des électrolytes céramiques mécaniquement flexibles et leurs procédés de fabrication
US20190273258A1 (en) * 2018-03-05 2019-09-05 Samsung Electronics Co., Ltd. Solid electrolyte for a negative electrode of a secondary battery and methods for the manufacture of an electrochemical cell
US20200083562A1 (en) * 2018-09-06 2020-03-12 Samsung Electronics Co., Ltd. Solid electrolyte, method of preparing the same, and secondary battery including the same
US20200243870A1 (en) * 2013-03-21 2020-07-30 University Of Maryland, College Park Ion conducting batteries with solid state electrolyte materials
US20210359338A1 (en) * 2020-05-18 2021-11-18 General Electric Company Solid state battery, ceramic electrolyte structure and methods of making

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080102337A1 (en) * 2005-02-28 2008-05-01 The Tokyo Electric Power Company, Incorporated Solid Oxide Type Fuel Battery Cell and Process for Producing the Same
US20200243870A1 (en) * 2013-03-21 2020-07-30 University Of Maryland, College Park Ion conducting batteries with solid state electrolyte materials
WO2018089430A1 (fr) * 2016-11-08 2018-05-17 Fisker Inc. Batteries li-ion tout solide comprenant des électrolytes céramiques mécaniquement flexibles et leurs procédés de fabrication
US20190273258A1 (en) * 2018-03-05 2019-09-05 Samsung Electronics Co., Ltd. Solid electrolyte for a negative electrode of a secondary battery and methods for the manufacture of an electrochemical cell
US20200083562A1 (en) * 2018-09-06 2020-03-12 Samsung Electronics Co., Ltd. Solid electrolyte, method of preparing the same, and secondary battery including the same
US20210359338A1 (en) * 2020-05-18 2021-11-18 General Electric Company Solid state battery, ceramic electrolyte structure and methods of making

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