GB2587585A - Rechargable lithium-ion battery with an anode structure containing a porous region - Google Patents

Rechargable lithium-ion battery with an anode structure containing a porous region Download PDF

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Publication number
GB2587585A
GB2587585A GB2100140.9A GB202100140A GB2587585A GB 2587585 A GB2587585 A GB 2587585A GB 202100140 A GB202100140 A GB 202100140A GB 2587585 A GB2587585 A GB 2587585A
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United Kingdom
Prior art keywords
porous
battery
region
porous layer
layer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
GB2100140.9A
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GB202100140D0 (en
GB2587585B (en
Inventor
Pereira De Souza Joel
Collins John
Sadana Devendra
W Bedell Stephen
Ott John
Johannes Petrus Hopstaken Marinus
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International Business Machines Corp
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International Business Machines Corp
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Filing date
Publication date
Priority claimed from US16/026,473 external-priority patent/US10777842B2/en
Priority claimed from US16/026,426 external-priority patent/US10833311B2/en
Priority claimed from US16/026,461 external-priority patent/US10833357B2/en
Priority claimed from US16/026,448 external-priority patent/US10833356B2/en
Application filed by International Business Machines Corp filed Critical International Business Machines Corp
Publication of GB202100140D0 publication Critical patent/GB202100140D0/en
Publication of GB2587585A publication Critical patent/GB2587585A/en
Application granted granted Critical
Publication of GB2587585B publication Critical patent/GB2587585B/en
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

Rechargeable lithium-ion batteries that have a high-capacity are provided. The lithium-ion batteries contain an anode structure that is of unitary construction and includes a non-porous region and a porous region including a top porous layer (Porous Region 1) having a first thickness and a first porosity, and a bottom porous layer (Porous Region 2) located beneath the top porous layer and forming an interface with the non-porous region. At least an upper portion of the non-porous region and the entirety of the porous region are composed of silicon, and the bottom porous layer has a second thickness that is greater than the first thickness, and a second porosity that is greater than the first porosity.

Claims (45)

1. A battery comprising: a lithium-containing cathode material layer; an anode structure of unitary construction and including a non-porous region and a porous region comprising a top porous layer having a first thickness and a first porosity, and a bottom porous layer located beneath the top porous layer and forming an interface with the non-porous region, wherein at least an upper portion of the non-porous region and the entirety of the porous region are composed of silicon, and wherein the bottom porous layer has a second thickness that is greater than the first thickness, and a second porosity that is greater than the first porosity; and an electrolyte region located between the top porous layer of the anode structure and the lithium- containing cathode material layer.
2. The battery of Claim 1 , wherein the top porous layer, the bottom porous layer, and the non-porous region are entirely composed of silicon.
3. The battery of Claim 2, wherein the silicon is single crystalline.
4. The battery of Claim 1 , wherein a lower portion of the non-porous layer is composed of doped silicon or a doped silicon germanium alloy having a germanium content of less than 10 atomic percent.
5. The battery of Claim 1 , wherein the first porosity of the upper porous layer has an average pore opening of less than 3 nm, and wherein the second porosity of the bottom porous layer has an average pore opening of greater than 3 nm.
6. The battery of Claim 1 , wherein the first thickness of the top porous layer is 50 nm or less.
7. The battery of Claim 1 , wherein the second thickness of the bottom porous layer is between 0.1 m to 20 pm.
8. The battery of Claim 1 , wherein the non-porous region is composed of p-doped silicon that is single crystalline.
9. The battery of Claim 1 , wherein the non-porous region and the porous regions are entirely comprised of p-type doped silicon.
10. The battery of Claim 1 , wherein the silicon is p-doped silicon having a p-type dopant concentration in a range of 1019 cm 3.
11. The battery of Claim 1 , wherein the silicon is boron-doped silicon.
12. The battery of Claim 1, further comprising an anode current collector contacting a surface of the non-porous region of the anode structure.
13. The battery of Claim 1, further comprising a cathode current collector electrode contacting a surface of the lithium-containing cathode material layer.
14. The battery of Claim 1, wherein the electrolyte region is composed of a solid-state electrolyte, a liquid electrolyte, a semi-solid electrolyte, an originally liquid then becoming solid electrolyte, a gel electrolyte, a polymer- containing electrolyte, a composite cathode/electrolyte combination, or any combination thereof.
15. The battery of Claim 1, wherein the electrolyte region is entirely composed of a solid-state electrolyte.
16. The battery of Claim 1, further comprising an interfacial additive material layer located between the top porous layer of the anode structure and the electrolyte region.
17. The battery of Claim 1, further comprising an interfacial additive material layer located between the electrolyte and the lithium-containing cathode material layer.
18. The battery of Claim 1, further comprising a first interfacial additive material layer located between the top porous layer of the anode structure and the electrolyte region, and a second interfacial additive material layer located between the electrolyte and the lithium-containing cathode material layer.
19. The battery of Claim 1, wherein the porous region including the top and bottom porous layers are patterned.
20. The battery of Claim 19, wherein the lithium-containing cathode material layer is patterned.
21. The battery of Claim 1 , wherein the porous region is located at the top, bottom or side of any three-dimensional structure.
22. The battery of Claim 1 wherein the lithium-containing cathode material layer is selected from a lithium- containing material containing grains having a grain size of less than 100 nm and a density of grain boundaries of
1 W -9 10 cm or greater, or a lithium-containing material having a columnar microstructure.
23. The battery of Claim 15 wherein the battery further comprises a seed layer located on a surface of the top porous layer of the anode structure, wherein the seed layer is a planar, conformal lithium-containing material.
24. A method of making a lithium battery anode structure, the method comprising: immersing a substrate including at least an upper portion that is composed of p-doped silicon in concentrated hydrogen fluoride while utilizing an anodization setup; applying an electrical current to the anodization setup; and anodizing the substrate electrochemically, wherein the anodizing provides a structure of unitary construction and including a non-porous region and a porous region comprising a top porous layer having a first thickness and a first porosity, and a bottom porous layer located beneath the top porous layer and forming an interface with the non-porous region, wherein at least an upper portion of the non-porous region and the entirety of the porous region are composed of silicon, and wherein the bottom porous layer has a second thickness that is greater than the first thickness, and a second porosity that is greater than the first porosity.
25. The method of Claim 24, further comprising cleaning the substrate prior to the immersing.
26. The method of Claim 24, further comprising rinsing the structure with deionized water and drying, after the anodizing.
27. The method of Claim 24, wherein an entirety of the substrate is composed of p-doped silicon.
28. The method of Claim 27, wherein the p-doped silicon is single crystalline.
29. The method of Claim 25, wherein the cleaning is performed by using a mixture of deionized water, ammonium hydroxide, and hydrogen peroxide (5:1 : 1 by volume) at a temperature from 60C to 80C, for a period in the range of five to thirty minutes, followed by rinsing in deionized water.
30. The method of Claim 24, wherein the concentrated hydrogen fluoride is a 49% hydrofluoric acid solution.
31. The method of Claim 24, wherein the electrical current is a constant current in a range of 1 mA/cm2 to 10 mA/cm2.
32. The method of Claim 24, wherein the anodizing of the substrate is performed at a temperature from 20°C to 30°C.
33. The method of Claim 32, wherein the anodizing of the substrate is performed at an electrical current that is less than or equal to 5 mA/cm2 for 10 seconds to 2000 seconds.
34. The method of Claim 24, wherein the top porous layer, the bottom porous layer, and the non-porous region are entirely composed of silicon.
35. The method of Claim 34, wherein the silicon is single crystalline.
36. The method of Claim 24, wherein a lower portion of the non-porous layer is composed of doped silicon or a doped silicon germanium alloy having a germanium content of less than 10 atomic percent.
37. The method of Claim 24, wherein the first porosity of the upper porous layer has an average pore opening of less than 3 nm, and wherein the second porosity of the bottom porous layer has an average pore opening of greater than 3 nm.
38. The method of Claim 24, wherein the first thickness of the top porous layer is 50 nm or less.
39. The method of Claim 24, wherein the second thickness of the bottom porous layer is between 0.1 m to 20 pm.
40. The method of Claim 24, wherein the non-porous region is composed of p-doped silicon that is single crystalline.
41. The method of Claim 24, wherein the non-porous region and the porous regions are entirely comprised of p- type doped silicon.
42. The method of Claim 24, wherein the silicon is p-doped silicon having a p-type dopant concentration in a range of 1019 cm·3
43. The method of Claim 24, wherein the silicon is boron-doped silicon.
44. The method of Claim 24, further comprising patterning the porous region including the top and bottom porous layers.
45. The method of Claim 24, wherein the porous region is formed at the top, bottom or side of any three- dimensional structure.
GB2100140.9A 2018-07-03 2019-06-18 Rechargeable lithium-ion battery with an anode structure containing a porous region Active GB2587585B (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US16/026,473 US10777842B2 (en) 2018-07-03 2018-07-03 Rechargeable lithium-ion battery with an anode structure containing a porous region
US16/026,426 US10833311B2 (en) 2018-07-03 2018-07-03 Method of making an anode structure containing a porous region
US16/026,461 US10833357B2 (en) 2018-07-03 2018-07-03 Battery structure with an anode structure containing a porous region and method of operation
US16/026,448 US10833356B2 (en) 2018-07-03 2018-07-03 Kinetically fast charging lithium-ion battery
PCT/IB2019/055075 WO2020008285A1 (en) 2018-07-03 2019-06-18 Rechargeable lithium-ion battery with an anode structure containing a porous region

Publications (3)

Publication Number Publication Date
GB202100140D0 GB202100140D0 (en) 2021-02-17
GB2587585A true GB2587585A (en) 2021-03-31
GB2587585B GB2587585B (en) 2021-08-25

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GB2100140.9A Active GB2587585B (en) 2018-07-03 2019-06-18 Rechargeable lithium-ion battery with an anode structure containing a porous region

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JP (1) JP7299924B2 (en)
CN (1) CN112400245A (en)
DE (1) DE112019002427T5 (en)
GB (1) GB2587585B (en)
WO (1) WO2020008285A1 (en)

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US11961958B2 (en) 2019-05-27 2024-04-16 International Business Machines Corporation 3D textured composite silicon anode and fluorinated lithium compound electrochemical cell
US11322787B2 (en) 2019-11-18 2022-05-03 International Business Machines Corporation Encapsulating in-situ energy storage device with cathode contact
US11876233B2 (en) 2020-02-20 2024-01-16 International Business Machines Corporation Thin film battery stacking
US11721801B2 (en) 2020-08-17 2023-08-08 International Business Machines Corporation, Armonk Low resistance composite silicon-based electrode
TWI792713B (en) * 2021-11-24 2023-02-11 芯量科技股份有限公司 Composite negative electrode structure
DE102022201392A1 (en) 2022-02-10 2023-08-10 Helmholtz-Zentrum Dresden - Rossendorf E. V. Implanting ions in a silicon based anode for secondary batteries

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Also Published As

Publication number Publication date
CN112400245A (en) 2021-02-23
JP2021529414A (en) 2021-10-28
WO2020008285A1 (en) 2020-01-09
GB202100140D0 (en) 2021-02-17
JP7299924B2 (en) 2023-06-28
GB2587585B (en) 2021-08-25
DE112019002427T5 (en) 2021-02-11

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