[미국특허]
Vitreous solid electrolyte sheets of Li ion conducting sulfur-based glass and associated structures, cells and methods
원문보기
IPC분류정보
국가/구분
United States(US) Patent
등록
국제특허분류(IPC7판)
H01M-010/0562
H01M-010/052
H01M-010/056
H01M-002/16
H01M-010/0525
출원번호
US-0954812
(2015-11-30)
등록번호
US-10164289
(2018-12-25)
발명자
/ 주소
Visco, Steven J.
Nimon, Yevgeniy S.
De Jonghe, Lutgard C.
Katz, Bruce D.
Nimon, Vitaliy
출원인 / 주소
POLYPLUS BATTERY COMPANY
대리인 / 주소
Weaver Austin Villeneuve & Sampson LLP
인용정보
피인용 횟수 :
0인용 특허 :
75
초록▼
A lithium ion-conductive solid electrolyte including a freestanding inorganic vitreous sheet of sulfide-based lithium ion conducting glass is capable of high performance in a lithium metal battery by providing a high degree of lithium ion conductivity while being highly resistant to the initiation a
A lithium ion-conductive solid electrolyte including a freestanding inorganic vitreous sheet of sulfide-based lithium ion conducting glass is capable of high performance in a lithium metal battery by providing a high degree of lithium ion conductivity while being highly resistant to the initiation and/or propagation of lithium dendrites. Such an electrolyte is also itself manufacturable, and readily adaptable for battery cell and cell component manufacture, in a cost-effective, scalable manner.
대표청구항▼
1. A standalone Li ion conductive solid electrolyte separator comprising: a freestanding substantially amorphous solid electrolyte wall structure that is dense, inorganic and highly conductive of Li ions, the wall structure comprising: i) a continuous Li ion conducting inorganic amorphous material p
1. A standalone Li ion conductive solid electrolyte separator comprising: a freestanding substantially amorphous solid electrolyte wall structure that is dense, inorganic and highly conductive of Li ions, the wall structure comprising: i) a continuous Li ion conducting inorganic amorphous material phase with room temperature Li ion conductivity ≥10−5 S/cm;ii) first and second opposing principal sides and associated surfaces; andiii) a microstructure devoid of contiguous crystalline grain boundaries and powder particle boundaries extending between the opposing principal side surfaces;wherein the inorganic amorphous material phase is a Li ion conducting sulfur-based glass having, S (sulfur) and Li (lithium) as constituent elements of the glass; andat least one more constituent element of the glass selected from the group consisting of P (phosphorous), B (boron), Ge (germanium), and Si (silicon);wherein the wall structure is a freestanding vitreous sheet of the Li ion conducting sulfur-based glass; andwherein the vitreous sheet has substantially parallel lengthwise edges. 2. The standalone Li ion conductive solid electrolyte separator of claim 1, wherein the area of the vitreous sheet is at least 100 cm2. 3. The standalone Li ion conductive solid electrolyte separator of claim 1, wherein the length of the vitreous sheet is at least 25 cm. 4. The standalone Li ion conductive solid electrolyte separator of claim 1, wherein the vitreous sheet has length (l) to width (w) area aspect ratio (l/w) of no less than 10, and the sheet width (w) is no less 1 cm. 5. The standalone Li ion conductive solid electrolyte separator of claim 1, wherein the first principal side comprises a liquid-like surface. 6. The standalone Li ion conductive solid electrolyte separator of claim 5, wherein the liquid-like first principal side surface lacks flaws having a flaw depth extension (Γ) of more than 5 μm. 7. The standalone Li ion conductive solid electrolyte separator of claim 6, wherein the liquid-like first principal side surface lacks flaws having a flaw depth extension (Γ) greater than 1% of the sheet thickness. 8. The standalone Li ion conductive solid electrolyte separator of claim 5, wherein the liquid-like first principal side surface is characterizable as having a threshold current density greater than 1 mA/cm2. 9. The standalone Li ion conductive solid electrolyte separator of claim 8, wherein the threshold current density is greater than 2 mA/cm2. 10. The standalone lithium ion conductive solid electrolyte separator of claim 5, wherein the liquid-like first principal side surface has average surface roughness Ra≤0.05 um. 11. The standalone lithium ion conductive solid electrolyte separator of claim 5, wherein the liquid-like first principal side surface has average surface waviness Wa≤5 μm. 12. The standalone Li ion conductive solid electrolyte separator of claim 5, wherein the first principal side surface is untouched by an abrasive solid surface. 13. The standalone Li ion conductive solid electrolyte separator of claim 12, wherein the second principal side surface is untouched by an abrasive solid surface. 14. The standalone Li ion conductive solid electrolyte separator of claim 1, wherein the first and second principal side surfaces of the vitreous sheet, in its virgin state as a solid, are untouched by a foreign solid body surface. 15. The standalone Li ion conductive solid electrolyte separator of claim 14, wherein the vitreous sheet, in its virgin state as a solid, has a uniform thickness no greater than 100 μm thick. 16. The standalone Li ion conductive solid electrolyte separator of claim 1, wherein the first and second principal sides of the vitreous sheet are essentially free of surface microvoids. 17. The standalone Li ion conductive solid electrolyte separator of claim 1, wherein the vitreous sheet is essentially free of internal micropores. 18. The standalone Li ion conductive solid electrolyte separator of claim 1, wherein the first principal side surface of the vitreous sheet of sulfur-based glass is chemically compatible in direct contact with Li metal. 19. The standalone lithium ion conductive solid electrolyte separator of claim 18, wherein the vitreous sheet has ASR of no more than 200 Ω-cm2, as measured using non-blocking lithium metal electrodes in direct contact with the first and second principal opposing side surfaces. 20. The standalone lithium ion conductive solid electrolyte separator of claim 19, wherein the sulfur-based glass comprises B (boron) as a constituent element and is substantially devoid of P (phosphorous). 21. The standalone Li ion conductive solid electrolyte separator of claim 1, wherein the sulfur-based glass is of the type selected from the group consisting of Li2S—YSn, Li2S—YSn—YOn, and combinations thereof; wherein Y is selected from the group consisting of Ge, Si, As, B, or P; and n=2, 3/2 or 5/2. 22. The standalone Li ion conductive solid electrolyte separator of claim 1, wherein the sulfur-based glass comprises Li2S as a glass modifier and one or more glass formers selected from the group consisting of P2S5, P2O5, SiS2, SiO2, B2S3 and B2O3. 23. The standalone Li ion conductive solid electrolyte separator of claim 1, further comprising electrically insulating edge-protector elements, which interface with the substantially parallel lengthwise edges of the vitreous sheet. 24. The standalone Li ion conductive solid electrolyte component of claim 1, wherein the vitreous sheet is in the form of a continuous web of sulfur-based glass having length >100 cm. 25. The standalone Li ion conductive solid electrolyte component of claim 24, wherein the continuous web is in the form of a coil. 26. A standalone Li ion conductive solid electrolyte separator comprising: a freestanding substantially amorphous solid electrolyte wall structure that is dense, inorganic and highly conductive of Li ions, the wall structure comprising: i) a continuous Li ion conducting inorganic amorphous material phase with room temperature Li ion conductivity ≥10−5 S/cm;ii) first and second opposing principal sides and associated surfaces; andiii) a microstructure devoid of contiguous crystalline grain boundaries and powder particleboundaries extending between the opposing principal side surfaces;wherein the inorganic amorphous material phase is a Li ion conducting sulfur-based glass having, S (sulfur) and Li (lithium) as constituent elements of the glass; andat least one more constituent element of the glass selected from the group consisting of P (phosphorous), B (boron), Ge (germanium), and Si (silicon);wherein the wall structure is a freestanding vitreous sheet of the Li ion conducting sulfur-based glass; andwherein the vitreous sheet of sulfur-based glass has a uniform thickness of no more than 100 μm. 27. A standalone Li ion conductive solid electrolyte separator comprising: a freestanding substantially amorphous solid electrolyte wall structure that is dense, inorganic and highly conductive of Li ions, the wall structure comprising: i) a continuous Li ion conducting inorganic amorphous material phase with room temperature Li ion conductivity ≥10−5 S/cm;ii) first and second opposing principal sides and associated surfaces; andiii) a microstructure devoid of contiguous crystalline grain boundaries and powder particle boundaries extending between the opposing principal side surfaces;wherein the inorganic amorphous material phase is a Li ion conducting sulfur-based glass having, S (sulfur) and Li (lithium) as constituent elements of the glass; andat least one more constituent element of the glass selected from the group consisting of P (phosphorous), B (boron), Ge (germanium), and Si (silicon);wherein the wall structure is a freestanding vitreous sheet of the Li ion conducting sulfur-based glass;wherein the vitreous sheet is essentially free of internal micropores; andwherein the vitreous sheet is wound about a spool for storage, the spool having diameter of no more than 20 cm. 28. A lithium battery cell comprising: a positive electrode;a negative electrode; anda solid electrolyte separator disposed between the electrodes, wherein the solid electrolyte separator is a standalone Li ion conductive solid electrolyte separator comprising:a freestanding substantially amorphous solid electrolyte wall structure that is dense, inorganic and highly conductive of Li ions, the wall structure comprising:i) a continuous Li ion conducting inorganic amorphous material phase with room temperature Li ion conductivity ≥10−5 S/cm;ii) first and second opposing principal sides and associated surfaces; andiii) a microstructure devoid of contiguous crystalline grain boundaries and powder particle boundaries extending between the opposing principal side surfaces. 29. The cell of claim 28, wherein the wall structure is a freestanding vitreous sheet of the Li ion conducting sulfur-based glass. 30. The cell of claim 29, wherein the vitreous sheet has substantially parallel lengthwise edges. 31. A method for making a standalone Li ion conductive solid electrolyte separator, the method comprising making a vitreous solid sheet of Li ion conducting sulfur-based glass; wherein the method for making the vitreous sheet comprises the steps of: a. forming a continuous fluid sheet of an inorganic sulfur-based glass at a temperature above Tg of the glass, the fluid sheet having substantially parallel lengthwise edges and a center portion having first and second opposing principal side surfaces;b. causing the continuous fluid sheet to flow with unbroken continuity;c. solidifying the continuous fluid sheet by cooling it to a temperature below Tg; wherein the solidified fluid sheet of sulfur-based glass is vitreous, substantially amorphous, conductive of Li ions, and of unbroken continuity. 32. The method of claim 31, wherein just prior to reaching a temperature at or below Tg, the first and second principal side surfaces are untouched by a foreign solid surface. 33. The method of claim 32, wherein the center portion of the fluid sheet has uniform thickness (t) selected from the group consisting of 250 μm
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