Patent Application
20220267166
The present disclosure generally relates to ionic conductors, and particularly to lithium-ion conductors.
Solid-state inorganic electrolytes provide many advantages in secondary battery design, including mechanical stability, no volatility, and ease of construction. However, H2S gas can be generated during decomposition of traditional sulfide solid-state inorganic electrolytes and traditional oxide solid-state inorganic electrolytes can have issues with formability due to hardness of the oxide.
The present disclosure addresses these issues with solid-state inorganic electrolytes, and other issues related to solid-state ionic conductors.
In one form of the present disclosure, a lithium-ion (Li-ion) conductor includes an inorganic compound with a chemical composition of Li2−3x+y−zFexOy(OH)1−yCl1−z, where x is greater than or equal to 0 and less than 1, y is greater than or equal to 0 and less than or equal 1, and z is greater than or equal to 0 and less than or equal 0.25. Also, the inorganic compound has a crystal structure that reflects or exhibits x-ray diffraction peaks with a 2θ between about 22.12° and about 24.12°, between about 31.97° and about 33.97°, between about 39.55° and about 41.55°, between about 46.46° and about 48.46°, between about 57.77° and about 59.77°, and between about 68.04° and about 70.04°.
In another form of the present disclosure, a Li-ion conductor includes an inorganic compound with a chemical composition of Li2−3x+y−zFexOy(OH)1−yCl1−z, where x is greater than or equal to 0 and less than 1, y is greater than or equal to 0 and less than or equal 1, and z is greater than or equal to 0 and less than or equal 0.25. Also, the inorganic compound has or exhibits a thermal decomposition temperature greater than 390° C. and has a crystal structure that reflects or exhibits x-ray diffraction peaks with a 2θ between about 22.12° and about 24.12°, between about 31.97° and about 33.97°, between about 39.55° and about 41.55°, between about 46.46° and about 48.46°, between about 57.77° and about 59.77°, and between about 68.04° and about 70.04°.
In still another form of the present disclosure, a Li-ion conductor includes an inorganic compound with a chemical composition of Li2−3x+y−zFexOy(OH)1−yCl1−z, where x is greater than or equal to 0 and less than 1, y is greater than or equal to 0 and less than or equal 1, and z is greater than or equal to 0 and less than or equal 0.25. Also, the inorganic compound has or exhibits a thermal decomposition temperature greater than 390° C., an ionic conductivity greater than about 1.0×10−4 S/cm at 25° C., and has a crystal structure that reflects or exhibits x-ray diffraction peaks with a 2θ between about 22.12° and about 24.12°, between about 31.97° and about 33.97°, between about 39.55° and about 41.55°, between about 46.46° and about 48.46°, between about 57.77° and about 59.77°, and between about 68.04° and about 70.04°.
These and other features of the nearly solvent-free combined salt electrolyte and its preparation will become apparent from the following detailed description when read in conjunction with the figures and examples, which are exemplary, not limiting.
The present teachings will become more fully understood from the detailed description and the accompanying drawings, wherein:
It should be noted that the figures set forth herein is intended to exemplify the general characteristics of the methods, algorithms, and devices among those of the present technology, for the purpose of the description of certain aspects. The figure may not precisely reflect the characteristics of any given aspect and are not necessarily intended to define or limit specific forms or variations within the scope of this technology.
The present disclosure provides inorganic Li-ion conductors with iron, oxygen, and chlorine. The inorganic Li-ion conductors (also referred to herein simply as “Li-ion conductors” and “Li-ion conductor”) have a composition of Li2−3x+y−zFexOy(OH)1−yCl1−z, where x is greater than or equal to 0 and less than 1, y is greater than or equal to 0 and less than or equal 1, and z is greater than or equal to 0 and less than or equal 0.25. In addition, the Li-ion conductors according to the teachings of the present disclosure provide a solid-state electrolyte and/or a positive electrode coating layer with increased ionic conductivity compared to solid-state electrolytes and/or positive electrode coating layers without the composition noted above.
Referring to
The mixture of the Li-halide and inorganic oxychloride ionic conductor are heat treated at 120 such that the Li-ion conductor is formed at 130. In some variations the mixture of the Li-halide and inorganic oxychloride ionic conductor are heated to temperatures above 100° C. for time periods greater than 12 hours.
Referring now to
The mixture of the chloride containing reagents 200, 202, . . . 220 are dissolved in a liquid to form a mixed chloride liquid solution at 240. The liquid can be any liquid in which the chloride containing reagents (e.g., FeCl3, MgCl2 and/or CaCl2) powders dissolve, e.g., deionized water.
Heat is applied to the mixed chloride liquid solution at 250 such that an inorganic oxychloride precipitates out of the mixed chloride solution and forms particles of the inorganic oxychloride at 260. In some variations, the mixed chloride liquid solution is heated to a temperature above 100° C., for example above 200° C. In variations where powders of one or more chlorides of Fe are mixed with powders of one or more chlorides of Mg and/or Ca, doped FeOCl in the form of (Fe1−xMx)O1−y(OH)yCl1−x precipitates out of the mixed chloride solution and forms particles of the (Fe1−xMx)O1−y(OH)yCl1−x at 260, where x is greater than 0 and less than or equal to 0.25, y is greater than or equal to 0 and less than or equal to 0.25.
In some variations, the mixed chloride liquid solution is heated in a container (e.g., a glass beaker) until most or all of the liquid evaporates and precipitated particles of the inorganic oxychloride (e.g., (Fe1−xMx)O1−y(OH)yCl1−x) remain in the container. In other variations, the mixed chloride liquid solution is poured onto a heated surface such that the liquid evaporates and precipitated particles of the inorganic oxychloride remain on the heated surface. It should be understood that the precipitated particles of the inorganic oxychloride can be ground using a mortar and pestle and/or a ball mill to ensure uniform inorganic oxychloride particle size and/or uniform chemical composition throughout the inorganic oxychloride.
In order to further describe the teachings of the present disclosure, but not limit scope thereof in any manner, one non-limiting example of synthesizing an inorganic oxychloride ionic conductor and one example of synthesizing a Li-ion conductor according to the teachings of the present disclosure are provided below.
Predefined portions of commercial reagent powders of FeCl3, MgCl2 and CaCl2 were weighed in an argon (Ar) glove box with a dew point of about −90° C. The weighed portions of the FeCl3, MgCl2 and CaCl2 powders were mixed together using a mortar and pestle and then dissolved in deionized water to form a mixed chloride liquid solution by pouring the mixed powders of FeCl3, MgCl2 and CaCl2 into a beaker containing the deionized water, and then placing the beaker in an ultrasonic cleaner. After the mixed powders of FeCl3, MgCl2 and CaCl2 were dissolved in the deionized water, the mixed chloride liquid solution was slowly poured into a glass beaker heated to about 200-300° C., which resulted in the evaporation of the deionized water and precipitation of dark red (Fe1−xMx)O1−y(OH)yCl1−x particles at the bottom of the glass beaker.
Powder of LiCl was mixed with powder of (Fe1−xMx)O1−y(OH)yCl1−x formed in Example 1 and heat treated at about 230° C. for about 40 hours in an Ar atmosphere to form powders of the ionic conductor Li2−3x+y−zFexOy(OH)1−yCl1−z. The powders of the Li-ion conductor were compressed into cylindrical pellets using uni-axial pressure and the cylindrical pellets were sandwiched between electrodes in the form of 0.05 mm thick gold foil to form electrochemical cells.
Referring to
Referring to
Still referring to
In view of the teachings of the present disclosure, it should be understood that a Li-ion conductor according to the teachings of the present disclosure exhibits enhanced cationic conductivity and/or thermal stability compared to traditional Li-ion conductors. In addition, in some variations a Li-ion conductor according to the teachings of the present disclosure is in the form of and/or part of a positive electrode coating layer 204 on a positive electrode 200 as illustrated in
The preceding description is merely illustrative in nature and is in no way intended to limit the disclosure, its application, or uses. As used herein, the phrase at least one of A, B, and C should be construed to mean a logical (A or B or C), using a non-exclusive logical “or.” It should be understood that the various steps within a method may be executed in different order without altering the principles of the present disclosure. Disclosure of ranges includes disclosure of all ranges and subdivided ranges within the entire range.
The headings (such as “Background” and “Summary”) and sub-headings used herein are intended only for general organization of topics within the present disclosure, and are not intended to limit the disclosure of the technology or any aspect thereof. The recitation of multiple forms or variations having stated features is not intended to exclude other forms or variations having additional features, or other forms or variations incorporating different combinations of the stated features.
As used herein the term “about” when related to numerical values herein refers to known commercial and/or experimental measurement variations or tolerances for the referenced quantity. In some variations, such known commercial and/or experimental measurement tolerances are +/−10% of the measured value, while in other variations such known commercial and/or experimental measurement tolerances are +/−5% of the measured value, while in still other variations such known commercial and/or experimental measurement tolerances are +/−2.5% of the measured value. And in at least one variation, such known commercial and/or experimental measurement tolerances are +/−1% of the measured value.
As used herein, the terms “comprise” and “include” and their variants are intended to be non-limiting, such that recitation of items in succession or a list is not to the exclusion of other like items that may also be useful in the devices and methods of this technology. Similarly, the terms “can” and “may” and their variants are intended to be non-limiting, such that recitation that a form or variation can or may comprise certain elements or features does not exclude other forms or variations of the present technology that do not contain those elements or features.
The broad teachings of the present disclosure can be implemented in a variety of forms. Therefore, while this disclosure includes particular examples, the true scope of the disclosure should not be so limited since other modifications will become apparent to the skilled practitioner upon a study of the specification and the following claims. Reference herein to one aspect, or various aspects means that a particular feature, structure, or characteristic described in connection with a form or variation is included in at least one form or variation. The appearances of the phrase “in one variation” or “in one form” (or variations thereof) are not necessarily referring to the same form or variation. It should be also understood that the various method steps discussed herein do not have to be carried out in the same order as depicted, and not each method step is required in each form or variation.
The foregoing description of the forms or variations has been provided for purposes of illustration and description. It is not intended to be exhaustive or to limit the disclosure. Individual elements or features of a particular form or variation are generally not limited to that particular form or variation, but, where applicable, are interchangeable and can be used in a selected form or variation, even if not specifically shown or described. The same may also be varied in many ways. Such variations should not be regarded as a departure from the disclosure, and all such modifications are intended to be included within the scope of the disclosure.
While particular forms or variations have been described, alternatives, modifications, variations, improvements, and substantial equivalents that are or may be presently unforeseen may arise to applicants or others skilled in the art. Accordingly, the appended claims as filed and as they may be amended, are intended to embrace all such alternatives, modifications variations, improvements, and substantial equivalents.
