Patent Grant
11018372
The disclosure relates to batteries and more particularly to alternatives to lithium ion batteries.
Lithium-ion batteries have become a leading technology for energy storage in portable and automotive applications. Other battery technologies have also been developed as alternatives to lithium-ion batteries. Sodium-ion batteries are an example of an alternative that uses sodium ions as charge carriers rather than lithium ions. Since sodium is more abundant than lithium, these batteries may be cheaper to produce than lithium-ion batteries.
The disclosure provides a sodium-ion battery, comprising an electrode having an active material; an interlayer comprising a passivation function; and a solid electrolyte medium in contact with a passivation layer. In one embodiment, the solid electrolyte material has the general formula Na3AX4 (A=P or Sb, X=S or Se). In a further embodiment, the interlayer comprises the general formula Na3AX4·8H2O (A=P or Sb, X=S or Se). In yet another or further embodiment, the solid electrolyte is Na3SbS4 and the interlayer is Na3SbS4·b 8H2O. In another embodiment, the electrode is a positive electrode or a cathode. In still another embodiment, the battery is made by preparing a solid electrolyte material; exposing the solid electrolyte material to an environment under conditions to obtain a passivation layer on the solid electrolyte material; placing/layering an anode Na metal electrode material in contact with the passivation layer; placing/layering a cathode electrode material in contact with the passivation layer; placing a current collector on each of the cathode electrode material and the anode Na metal electrode material. In another embodiment, the cathode material is a carbon or graphite. In still another embodiment, the current collector material is Cu, Al, or steel. The disclosure also provides a system comprising a batter of the disclosure and electronics for controlling the discharge of the battery.
As used herein and in the appended claims, the singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a sodium ion” includes a plurality of sodium ions and reference to “the electrode material” includes reference to one or more electrode materials and equivalents thereof known to those skilled in the art, and so forth.
Also, the use of “or” means “and/or” unless stated otherwise. Similarly, “comprise,” “comprises,” “comprising” “include,” “includes,” and “including” are interchangeable and not intended to be limiting.
It is to be further understood that where descriptions of various embodiments use the term “comprising,” those skilled in the art would understand that in some specific instances, an embodiment can be alternatively described using language “consisting essentially of” or “consisting of.”
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood to one of ordinary skill in the art to which this disclosure belongs. Although any methods and reagents similar or equivalent to those described herein can be used in the practice of the disclosed methods and compositions, the exemplary methods and materials are now described.
All publications mentioned herein are incorporated herein by reference in full for the purpose of describing and disclosing the methodologies, which are described in the publications, which might be used in connection with the description herein. With respect to any term that is presented in one or more publications that is similar to, or identical with, a term that has been expressly defined in this disclosure, the definition of the term as expressly provided in this disclosure will control in all respects.
The increasing demand for high-quality rechargeable batteries has promoted the development of low-cost alternatives to lithium batteries. Sodium (Na) batteries are particularly promising in this regard. Extremely high energy densities in sodium batteries can be attained if cells utilizing metallic sodium anodes can be successfully constructed. However, the usage of Na metal anodes requires the suppression of dendritic Na growth during battery operation, which if such dendritic growth occurs can lead to catastrophic failure. The use of a ceramic solid-state electrolyte membrane in lieu of the commonly employed liquid electrolyte is a promising solution that can result in greatly enhanced battery safety.
Thanks to the high room temperature ionic conductivity and low grain-boundary resistance of sulfide and selenide compounds, Na3AX4 (A=P or Sb, X=S or Se) have attracted significant attention as excellent candidates for electrolytes in solid state sodium metal batteries. Among these superionic conductors, Na3SbS4 was found to exhibit the highest Na-ion conductivity of 3 mS cm−1. However, it is observed that all Na3AX4 are not chemically stable against Na metal anode. This aligns well with computational results, which predict all Na3AX4 solid electrolytes (SE) are incompatible with Na metal and will spontaneously decompose into Na2X and Na3A. The continuous decomposition of Na3AX4 generates a growing mixed-conducting interphase (MCI), which can substantially degrade the long-term cycling performance of the solid-state battery.
The disclosure provides a stable solid electrolyte-Na interface (permeable to ions but insulating to electrons) engineered by introducing selective elements in the Na conductor which react to form passivating interfaces. Using advanced first-principles computational tools, which accurately predict ionic mobility and decomposition products, the disclosure identified compounds predicted to form favorable interfaces while also exhibiting high Na-ion conductivity. This led to the identification of hydrate based compounds as a class of materials which could form passivating interfaces with Na metal, because the reaction of hydrates with Na metal will almost always produce compounds such as NaH, Na2O and/or NaOH, which are known to be ionically conductive and electronically insulating on the basis of both experimental measurements and theoretical modeling.
The disclosure provides a hydrate/passivation layer on the SE to provide a protection layer between the Na metal and the SE. For example, the disclosure demonstrates that Na3SbS4.8H2O can form a stable and passivating solid electrolyte interphase (SEI), and can be used as a protection layer between Na metal and the solid-state electrolyte. The fast ionic conductivity of the SEI permits facile Na-ion transport, and the electronically insulating nature of the SEI inhibits electronic transport and further decomposition of Na3SbS4.8H2O, preventing the growth of the interface. The disclosure demonstrates that Na3SbS4.8H2O can be synthesized with a standard solid-state reaction. The disclosure also shows that using Na3SbS4.8H2O as a protection layer between the Na3SbS4 solid electrolyte and Na metal, a stable SEI with smaller interfacial resistance can be generated. The “hydrate-coated” solid electrolyte (e.g., Na3SbS4SE) delivers much higher stability against Na metal and enables better cycling of the Na metal symmetric cell compared with that of any non-hydrated Na3AX4 conductor as the SE. The results demonstrate the presence of both the protection layer of Na3SbS4.8H2O and the passivating SEI in the post-operando solid-state symmetric cell after more than 25 hours of cycling and 10 days of resting.
The moisture stability of Na3AX4 has previously been characterized, but has never been studied in the context of the hydration process and the formation of a passivating SEI of the hydrate phases. The disclosure enables a passivating and stable SEI via a reaction at the anode/SE interface—no anode modifications are needed. This achievement comes from the understanding of the newly discovered intermediate hydrate phase Na3SbS4.8H2O. From this particular case, a general strategy for SE protection can be derived: the inclusion of a hydrated protection layer prevents SE decomposition to mixed-conducting phases by reacting with the Li/Na metal anode to form products which are electronically insulating while still permitting Li/Na ion transport. One application of the disclosure will be a stable interface between the SE and metal electrode in Li-ion and Na-ion batteries. This disclosure also opens up a window for chemistry using other atmospheres (i.e. CO2, SO2, HCl, CH3OH, etc.) to perform surface treatment of the SE to form a protection layer.
The disclosure demonstrates a stabilized interface between the sulfide conductor Na3SbS4 and Na metal by the formation of NaH and Na2O through air exposure of the solid electrolyte pellet for a certain duration. The fast phase transformation between Na3SbS4, Na3SbS4·8H2O, and Na3SbS4·9H2O in ambient air at room temperature suggests the fast reaction kinetics of water uptake and release, which may have led to the generation of NaH and Na2O over other products from the reduction of Sb when the hydrated compounds contacted Na metal. In fact, the stability between Na3SbS4 and Na metal might have been achieved accidentally without realizing the effect of hydrate protection.
The battery can be included in a system that includes electronics in electrical communication with the battery. The electronics can monitor and control discharge and/or charging of the battery. For instance, the electronics can stop discharge of the battery in response to the voltage of the battery falling below a voltage threshold. Suitable voltage thresholds include, but are not limited to, thresholds less than 2.0 V.
Suitable electronics include, but are not limited to, firmware, hardware and software or a combination thereof. Examples of suitable electronics include, but are not limited to, analog electrical circuits, digital electrical circuits, processors, microprocessors, digital signal processors (DSPs), computers, microcomputers, ASICs, and discrete electrical components, or combinations suitable for performing the required control functions. In some instances, the electronics include one or more memories and one or more processing units such as a CPU. The one or more memories can include instructions to be executed by the processing unit during performance of the control and monitoring functions.
To synthesize Na3SbS4.8H2O, Na2S (Alfa Aesar, 99.8%), antimony (Sigma-Aldrich, 99.5% trace metals basis), and sulfur (Sigma-Aldrich, 99.5%) were used as precursors. A stoichiometric amount of powder precursors was mixed in an argon-filled glovebox. The resulting mixture (˜1 g) was then placed into a boron-nitride (BN) tube (3 mm inner diameter and 4 mm outer diameter), which was wrapped in aluminum foil, with the open end sealed with a stainless-steel Swagelok cap (⅜ in.). This tube was transferred into a sealed alumina tube furnace, which was purged with a pre-dried Ar gas (oxygen/moisture traps, model MT200-4-D, Agilent). The furnace was quickly ramped to 550° C. within ˜30 min, and was held at the same temperature for 17 h to complete the reaction. During the reaction, a continuous flow of argon gas with a flow rate of approximately 50 mL min−1 was used. The resulting products were collected after the furnace was naturally cooled down to room temperature, and were transferred immediately into the glovebox and manually ground into powder. The resulting powder (Na3SbS4) was exposed to ambient air (humidity˜68%) for 5 mins under continuous grinding with a mortar and pestle. Final products were collected and transferred into the glovebox for further characterization.
To observe the process of the phase transformation from Na3SbS4 to Na3SbS4.8H2O, X-ray diffraction (XRD) patterns were collected from the Na3SbS4 powder sample at various times during 120 minutes of air exposure. XRD experiments were performed at beamline 11-ID-B at the Advanced Photon Source (APS) of Argonne National Laboratory and utilized a constant wavelength of 0.1432 Å. The use of high-energy X-rays (E=86.57 keV) minimizes absorption effects. Due to the moisture sensitivity of Na3SbS4.8H2O, the as-prepared powder was packed and sealed into a 0.435 in. diameter Kapton capillary. For structure determination of Na3SbS4.8H2O, the Rietveld refinements were performed using the TOPAS 5.0 software package (Bruker).
To investigate the effect of Na3SbS4.8H2O on the improvement of the Na/Na3SbS4 interface, symmetric Na/Na3SbS4/Na cells with and without a Na3SbS4.8H2O protection layer were prepared and evaluated by Electrochemical Impedance Spectroscopy (EIS) to examine the interfacial resistance. To prepare the samples for EIS and electrochemistry analysis, ˜140 mg of Na3SbS4 powder was cold pressed under a pressure of ˜1.5 tons for 5 min into a pellet within an in-house designed pressure cell (7.7 mm inner diameter) in an argon glovebox. The resulting pellet (˜1 mm of thickness) was exposed to ambient air (humidity ⊇68%) for ˜5 min to achieve a hydrate coating (Na3SbS4.8H2O) on the Na3SbS4 pellet. Two metallic Na foils (6 mm diameter and <50 μm thickness) were then carefully attached on both sides. Both cells were assembled under an Ar atmosphere with otherwise identical procedures and used Na3SbS4 from the same batch of sintered powder to maximize consistency. Samples were measured with EIS at room temperature (˜25° C.) immediately after cell assembly. The EIS measurements were performed with a Solartron MTS system. The impedance data were collected from 1 MHz to 100 mHz with a D.C. voltage amplitude of 10 mV. The symmetric cells were then cycled with a constant current density of 0.1 mA/cm2 at room temperature for 25 hours using an Arbin battery cycler (model MSTAT). During cycling, the current direction was reversed every 30 mins. A spring pressure (˜3 MPa of pressure) was held within the pressure cells during cycling.
For phase determination of the products in the Na/SE interface, the spatially resolved post-operando X-ray diffraction patterns of the symmetric cells were collected at beamline 11-ID-B at APS using the Radially Accessible Tubular In-situ X-ray (RATIX) cell adapted for X-ray transmission. Cells were prepared in an Ar atmosphere glovebox using the same materials as for the pressure cell measurements. The Na3SbS4 pellets (3 mm diameter and ˜0.05 cm in thickness) with and without a Na3SbS4.8H2O protective layer were sandwiched between Na metal (1 mm diameter and <0.005 cm in thickness) and then sealed by Kapton tape. The assembled RATIX cells were cycled under the same conditions and were allowed to rest for 7 days before XRD measurements. The RATIX cell was oriented perpendicularly to the X-ray beam (λ=0.1432 Å). The detector was positioned at a distance of 95 cm from the sample. To increase the mapping resolution, the size of the beam was reduced to 50 μm in the cell (vertical) direction, but remained large (500 μm) in the perpendicular (horizontal) direction. The acquisition time for each diffraction pattern was 1 s, and diffraction patterns were measured consecutively at 11˜12 positions from top to bottom of the cell (
Background measurements were taken using identical cells, but without the testing materials present. A CeO2 standard was used to determine the sample geometry and the sample-to-detector distance. The data were integrated to a function of intensity vs. 2θ using FIT2D. Standard corrections (background, Compton scattering, detector effects) were applied, and Rietveld refinements were performed using the TOPAS 5.0 software package (Bruker).
X-ray diffraction (XRD) patterns in
EIS profiles of the symmetric Na/Na3SbS4 cells with and without a hydrate coating are shown in
To further investigate the impedance and ion transport properties of the Na/Na3SbS4 interface, D.C. Na plating and stripping experiments were carried out by electrochemically cycling the symmetric cells at a constant current. In this way, electrochemically deposited fresh Na metal was continuously generated during cycling which would continue reacting with Na3SbS4 if the SEI is not perfectly passivating. As shown in
The formation of a stable interface is due to the production of Na2O and NaH, which only occur as a result of reaction with the hydrated SE (Table 1). Using the same thermodynamic methodology as the one applied above, the Na2O and NaH, both wide-bandgap electronic insulators, were calculated to be stable against Na metal. Furthermore, prior experimental and theoretical works indicate that these phases exhibit relatively high Na+ conductivity. The formation of Na2O and NaH likely yields an ideal passivating interface (high ionic conductivity and electronically insulating). It is also believed that the growth of the interface impedance is positively correlated with the fraction of the mixed conducting phase in the decomposition products, e.g., Na3Sb in the current system. Since the molar ratio of Na3Sb sharply decreases from approximately 20% to 3% when the hydrate protection is used based on calculation results in Table 1, the interface impedance growth is expected to be much slower.
Spatially resolved in-depth post-operando XRD patterns for both the non-coated and hydrate-coated symmetric cells are shown in
Similarly, the XRD patterns containing the information of the Na/Na3SbS4 (hydrate protected) interfaces were colored in green, and the patterns for bulk Na3SbS4 solid electrolyte is colored in grey in
This application claims the benefit of U.S. Provisional Patent Application Ser. No. 62/640,943, filed Mar. 9, 2018, the disclosures of which are incorporated herein by reference.
| Number | Name | Date | Kind |
|---|---|---|---|
| 20140099539 | Yamazaki | Apr 2014 | A1 |
| 20140205883 | Wang | Jul 2014 | A1 |
| 20180241026 | Shibutani | Aug 2018 | A1 |
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| Tian et al., Reactivty-Guided Interface Design in Na Metal Solid State Batteries, Joule, 3, 1037-1050, Apr. 17, 2019 (Year: 2019). |
| Xiao et al., “Understanding interface stability in solid-state batteries,” Nature Reviews | Materials, www.nature.com/natrevmats, Published online Dec. 9, 2019 (Year: 2019). |
| Number | Date | Country | |
|---|---|---|---|
| 20190280326 A1 | Sep 2019 | US |
| Number | Date | Country | |
|---|---|---|---|
| 62640943 | Mar 2018 | US |
