Patent Application
20230227327
Aspects of the present invention relate to cathode materials for lithium-ion batteries, and more particularly, to lithium-rich lithium nickel manganese oxide cathode active materials, and methods of making the same.
Cobalt containing cathode material in lithium-ion batteries accounts for substantial fraction of the cost of a contemporary battery cell, and the cobalt is a key contributor to the cost. Cobalt has supply chain complexities that make it a volatile commodity. As such, there is a need for reliable cobalt-free lithium-ion battery cathode materials.
According to various embodiments, a method includes sintering a lithium-rich metal oxide (LRMO) material at a sintering temperature to form a sintered LRMO material and quenching the sintered LRMO material from the sintering temperature to room temperature in less than 500 milliseconds to form a quenched LRMO material represented by a chemical formula Lix(MnyNi1-y)2-xO2, where x is greater than 1.05 and less than 1.25, and y ranges from 0.95 to 0.1.
According to various embodiments, a method include thermally decomposing a precursor material using microwave radiation to form a thermally decomposed lithium-rich metal oxide (LRMO) material, sintering the thermally decomposed LRMO material to form a sintered LRMO material, and quenching the sintered LRMO material to form a quenched LRMO material represented by a chemical formula: Lix(MnyNi1-y)2-xO2, where x is greater than 1.05 and less than 1.25, and y ranges from 0.95 to 0.1.
According to various embodiments, a cathode electrode active material is represented by a chemical formula: Lix(MnyNi1-y)2-xO2, where x is greater than 1.05 and less than 1.25, and y ranges from 0.95 to 0.1. The active material comprises layered hexagonal and monoclinic phases. The active material exhibits at least one of: a (106)+(102):(101) x-ray diffraction peak intensity ratio of greater than 0.32; delivery of at least a 165 mAh/g specific capacity at a C/20 rate on first discharge when included in a lithium-ion battery; less than 10% loss in average discharge voltage at a C/20 rate after 100 charge/discharge cycles when included in the lithium-ion battery; and/or less than 10% capacity fade over 100 C/5 charge/discharge cycles when included in the lithium-ion battery.
The accompanying drawings, which are incorporated herein and constitute part of this specification, illustrate example embodiments of the invention, and together with the general description given above and the detailed description given below, serve to explain the features of the invention.
As set forth herein, various aspects of the disclosure are described with reference to the exemplary embodiments and/or the accompanying drawings in which exemplary embodiments of the invention are illustrated. This invention may, however, be embodied in many different forms and should not be construed as limited to the exemplary embodiments shown in the drawings or described herein. It will be appreciated that the various disclosed embodiments may involve particular features, elements or steps that are described in connection with that particular embodiment. It will also be appreciated that a particular feature, element or step, although described in relation to one particular embodiment, may be interchanged or combined with alternate embodiments in various non-illustrated combinations or permutations.
The various embodiments will be described in detail with reference to the accompanying drawings. Wherever possible, the same reference numbers will be used throughout the drawings to refer to the same or like parts. References made to particular examples and implementations are for illustrative purposes, and are not intended to limit the scope of the invention or the claims.
Ranges can be expressed herein as from “about” one particular value, and/or to “about” another particular value. When such a range is expressed, examples include from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about” or “substantially” it will be understood that the particular value forms another aspect. In some embodiments, a value of “about X” may include values of +/- 1% X. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.
According to various embodiments, a method of quickly and inexpensively forming a crystallographically-stable, highly durable, cobalt-free, lithium-rich metal oxide (LRMO) material is provided. In some embodiments, the LRMO material may be a lithium-rich, lithium manganese nickel oxide material represented by the following general Formula 1:
wherein x is greater than 1.0 and less than 1.25, and y ranges from 0.95 to 0.1, for example from about 0.8 to 0.5.
In some embodiments, the LRMO material may be a lithium-rich, lithium manganese nickel oxide material represented by the following Formula 2:
wherein x ranges from 0.1 to 0.4.
The LRMO material in its pristine state (e.g., before it is charged for the first time), may have distinct hexagonal (e.g., rhombohedral) and monoclinic phases. Thus, the LRMO material may be represented by the expression: (1-x)[Li2MnO3] * x [LiMnaNi(1-a)O2], wherein the first part of this expression denotes the relative molar amount of the monoclinic phase (1-x), while the second part of this expression denotes the relative molar amount of the rhombohedral phase (x). The molar fraction of the rhombohedral phase, “x”, commonly ranges between 0.8 and 0.95, while “a” ranges from 0.6 to 0.9. In some embodiments, the two phases may be disposed in a layered structure.
Various embodiments provide LRMO materials that exhibit high (e.g., > 240 mAh/g) specific capacities and high functional voltage windows (e.g., 2.0 - 4.8 V), when used as an active material of a cobalt-free cathode.
According to various embodiments, methods of forming LRMO materials include rapid thermal processing and rapid (e.g., less than 10 seconds) or ultra-rapid (e.g., less than 500 milliseconds) quenching that result in a LRMO material having a superior crystal structure with a desired atomic order/disorder. These features may provide unexpectedly robust long-term stability and performance when used as a cathode active material.
Conventional LRMO materials are generally unsuitable for use as a cathode active material due to having a low rate capability and poor capacity retention, which are believed to result from structural instability due to oxygen losses, transition metal ion migration during use, and possible manganese dissolution. The two most common aging mechanisms manifest as a fade in the average discharge voltage as the material slowly re-organizes into a predominant spinel structure, and loss in capacity over cycling due mechanical and/or chemical degradation of the material.
LRMO materials may be synthesized from precursor materials by a variety of methods. The following Table 1 includes particular methods that may be used to synthesize LRMO materials, including precursor synthesis, precursor materials, quenching methods, performance metrics, and discharge capacity (DC) of LRMO material cathodes.
As shown in Table 1, the three main synthetic routes for LRMO materials include precipitation followed by combustion, hydrothermal synthesis, and sol-gel solution production followed by intermediate temperature decomposition and high temperature thermal processing (e.g., calcination, annealing, sintering).
As can be seen in Table 1, the number of investigations exploring the effects of nickel composition on the performance LRMO cathodes has decreased over time; with few studies exploring multiple nickel compositions or nickel compositions below x = 0.2 in cathodes having the formula Li[NixLi((⅓-2x/3)Mn(⅔-x/3)]O2. Table 1 also shows that there are significant inconsistencies in synthetic routes employed across studies. Additionally, there are few studies that perform a detailed comparative assessment relating the effects of synthetic approach to performance of LRMO cathodes. In LRMO materials, the ordering and disordering of transition metals may be important, and both composition and synthetic techniques may provide mechanisms for influencing the degree of structural order and disorder. The electrochemical behaviors these compositional and synthetic changes could impose, such as different defect concentrations for example, may lead to pronounced effects on the properties of LRMO cathodes.
Without wishing to be bound by a particular theory, it is believed that when a sample is quenched in liquid nitrogen the particles are immediately shielded by an insulating envelope of nitrogen gas, similar to the Leidenfrost effect, which significantly reduces heat transfer rate. It is believed that in the prior art, lithium containing cathode materials for lithium ion batteries are not brought in contact with moisture because water leaches out lithium from such cathode materials and forms a lithium hydroxide coating on the materials. Furthermore, water is known to cause malfunctions in lithium ion batteries, such as lithium-ion batteries which contain lithium iron phosphate cathode materials.
While not wishing to be bound to a particular theory, the present inventors believe that the relatively slow conventional quenching and cooling process result in agglomeration of metal oxides, thereby forming segregated nickel oxide and lithium manganese oxide phases. In particular, nickel oxide phase may be concentrated on the surface of LRMO material particles (e.g., crystallites). It is believed that this surface nickel oxide agglomeration is at least partially responsible for the chemical instability of conventional LRMO active materials.
In contrast, the present inventors have unexpectedly determined that water quenching does not negatively affect the LRMO cathodes and does not cause lithium leaching from such LRMO cathodes. It is believed that water quenching results in vaporization in the form of bubble nucleation and dissipation, which actually increases the rate of heat transfer. As such, it is believed that water quenching should have a rate of heat transfer that can be approximated as two orders of magnitude greater than liquid nitrogen quenching. Further, water and additives solvated into it (i.e., other materials that may be dissolved in the water) can both react with the high temperature LRMO as it quenches to create advantageous surface terminations and/or coatings that enhance electrochemical stability and durability when used in a lithium-ion battery.
Additionally, in many of the prior art quench routes described above, the quenching is done on pressed sintered or partially sintered pellets of the material that are intact as larger bodies (e.g., having a width on the order of centimeters). In contrast, in embodiments of the present disclosure, the quenching is performed on loose and/or milled powder with particles that are in shapes agglomerates that are 20 microns or less in average diameter, such as 0.1 to 20 microns, for example, 0.1 to 1 microns or 1 to 20 microns, in average diameter, such that when the particles contact the quenching liquid (e.g., water) all of the material cools rapidly and at approximately the same rate. Each agglomerate is composed of crystallites having an average size ranging from about 25 nm to about 500 nm, such as 50 nm to 200 nm. Each crystallite may comprise a single crystal of the LRMO material. The crystallites may be partially fused together in the agglomerate or fully fused together in the agglomerate. If the crystallites are fully fused in the agglomerate (i.e., in a powder particle), then each crystallite comprises a single crystal grain of the powder particle which is separated from other single crystal grains in the same powder particle by grain boundaries. The average crystal grain size of the powder particles may range from about 25 nm to about 500 nm, such as 50 nm to 200 nm. The agglomerates may be relatively porous, which allows the water to reach the crystallites inside the agglomerate.
According to various embodiments, a LRMO cathode active material may be formed by thermally processing (e.g., sintering, calcining, and/or annealing) and quenching the LRMO material powder. In particular, the thermal processing may include a high-temperature process where the LRMO material may be heated to a process temperature ranging from about 800° C. to about 1000° C., such as from about 850° C. to about 950° C., or about 900° C. The thermal processing may be carried out in any suitable thermal processing apparatus, such as a furnace, for example a tube furnace, muffle box furnace, etc., In some embodiments, the thermal processing may optionally include one or more low-temperature precursor decomposition (e.g., firing) processes where the LRMO material is heated to a temperature above room temperature and below 800° C. For example, the firing may include heating the LRMO material to a temperature ranging from about 450° C. to about 550° C., such as about 500° C., prior to the high-temperature process.
According to various embodiments, the quenching process may include transferring the heated LRMO material to a quench bath. For example, the LRMO material may be dropped directly into from the thermal processing apparatus into the quench bath.
In prior art methods, the LRMO material may slowly cool during transfer from the furnace. For example, the transfer process may take up to about 10 seconds, during which the temperature of the LRMO material may be slowly reduced. The present inventors have determined that slow cooling prior to entering the quench bath may result in undesirable changes to the crystal structure of the sintered LRMO material. In other words, the temperature at which the sintered LRMO material enters the quench bath may be important to providing a desired crystal structure. For example, slow cooling may result in a less desirable crystal structure.
According to various embodiments, the transfer process may be configured such that the sintered LRMO material enters the quench bath after a sintering process at a temperature of at least 800° C., such as a temperature ranging from 800° C. to 950° C., or from about 850° C. to about 925° C., or about 900° C. For example, the transfer time from the thermal processing apparatus to the quench bath may be limited to 10 seconds or less, such as 1 seconds or less, such as less than 0.5 seconds, or 0.2 seconds or less. Thus, the sintered LRMO material is cooled from the thermal processing temperature (e.g., from the sintering temperature of at least 800° C., such as a temperature ranging from 800° C. to 950° C., or from about 850° C. to about 925° C., or about 900° C.) to room temperature (e.g., 25° C.) in 10 seconds or less, such as less than 0.5 seconds, including 0.2 seconds or less. Herein, an “ultra-rapid quenching process” may have a cooling time of less than 0.5 seconds, such as 0.2 seconds or less, for example 0.1 to 0.2 seconds, and a “rapid quenching process” may have a cooling time of 10 seconds or less, such as from 0.5 seconds to 10 seconds.
The sintered LRMO powder particles may be quenched in the quench bath at an average rate of at least 50° C./second, such as 50° C./second to 10,000° C./second. For example, the sintered LRMO powder particles may be quenched at a rate of 87.5° C./second to 8750° C./second, such as at least 1750° C./second, for example 1750° C./second to 8750° C./second, including 4375° C./second to 8750° C./second. Thus, the sintered LRMO material may be quenched from a temperature between the thermal processing temperature (e.g., sintering temperature) of at least 800° C. to the temperature of the quench bath (e.g., room temperature water bath at 25° C.) in 10 seconds or less, such as in less than 500 milliseconds, including 400 milliseconds or less, 300 milliseconds or less, or 200 milliseconds or less. For example, the quenching may occur in from 100 milliseconds to 400 milliseconds, or from 100 to 200 milliseconds.
The quench bath may comprise a high heat capacity liquid solvent having a vaporization temperature of below about 200° C. For example, the quench bath may comprise a solvent, such as water, an oil, and/or an alcohol. In some embodiments, the quench bath may comprise additives configured to modify the surface of the LRMO material during quenching to improve long term chemical stability of the material. The additive may comprise an acid, an alcohol and/or a dissolved carbon species, such as the acid, the alcohol or the carbon species dissolved in water.
For example, the quench bath may be an aqueous quenching solution that includes from about 0.01 to about 1.0 moles per liter, such as from about 0.1 to 1.0 moles per liter, or from about 0.5 to 1.0 moles per liter, of an acid additive, such as sulfuric acid, hydrochloric acid, nitric acid, oxalic acid, citric acid, acetic acid, phosphoric acid, orthophosphoric acid, combinations thereof, or the like. The acid may be configured to stabilize the surface of the LRMO particles by reacting with and/or passivating dangling bonds and/or OH terminal groups of the LRMO power particles that are being quenched in the water containing the acid additive.
In some embodiments, the acid quenching may result in the formation of a spinel structure (e.g., surface layer) on the surfaces the quenched LRMO powder particles. The spinel structure may form a framework that stabilizes the particles and provides three-dimensional pathways for lithium diffusion. In particular, it is believed that the acid may result in an exchange of Li ions of the particles with H ions of the acid, and a subsequent structural transformation of the surface of the particles, resulting in the formation of the spinel surface layer.
In another embodiment, the quenching solution may include an alcohol and/or a carbohydrate additive in addition to or in place of the acid additive. For example, the alcohol may include isopropyl alcohol or another alcohol, and the carbohydrate may include a sugar, such as fructose, galactose glucose, lactose, maltose, sucrose, combinations thereof, or the like. In some embodiments, the quenching solution may include from about 0.01 to about 1.0 moles per liter, such as from about 0.1 to 1.0 mole per liter, or from about 0.5 to 1.0 mole per liter, of the carbohydrate additive. The carbohydrates may form an intimate amorphous carbon coating on the surface of the LRMO powder particles during the quenching process in water containing the carbohydrate particle. The carbon coating may be permeable to Li ions but may be impermeable to an electrolyte of the Li-ion battery. The carbon coating may also permit volumetric changes in the LRMO crystallites to occur during charging and discharging of the battery.
The rapid or ultra-rapid quenching processes may produce a quenched LRMO material having a crystal structure that provides unexpected robustness and electrical characteristics. Specifically, the degree of crystalline order in the quenched LRMO material (e.g., lithium-rich lithium manganese nickel oxide) that is produced by the quenching processes may provide performance characteristics that are suited for use as a cathode active material of a lithium-ion battery that provides energy density and charge storage stability characteristics that are similar to that of cathodes that include cobalt-containing, high nickel-content, active materials.
The quenching processes may produce a quenched LRMO material powder having a desired crystal structure and particle size. For example, the sintered LRMO material being quenched may be a loose powder having an average particle size of about 1 µm or less, such as an average particle size ranging from about 0.02 µm to about 1 µm, or from about 0.05 µm to about 0.5 µm. The quenched LRMO material may include crystal phases and/or crystallites having an average crystal size ranging from about 25 nm to about 500 nm, such as from about 50 nm to about 300 nm, in some embodiments. Each powder particle may comprise one crystallite or more than one crystallite. The loose sintered and quenched powder particles may be incorporated into a binder (e.g., carbon binder) to form a cathode electrode for a Li-ion battery.
The quenched LRMO material is dried to form a LRMO active material (e.g., the thermally processed and quenched loose powder particles) may have a hexagonal primary phase and a monoclinic secondary phase. Thus, the ratio of the hexagonal phase content to monoclinic phase content is greater than 1, such as at least 2, for example 2 to 20. For example, the sintered and quenched LRMO material (e.g., dried active material) may have a superlattice structure including hexagonal primary phase layers separated by interlayers of the monoclinic secondary phase. Alternatively, the sintered and quenched LRMO material may include a hexagonal phase matrix containing monoclinic phase nano-zones (i.e., areas having a width of less than a micron). Mn and Ni may be homogenously distributed within the crystal structure of the LRMO material (e.g., excess Mn, Ni and Li are homogenously and uniformly distributed on the transition metal crystal lattice sites). For example, crystalline particles of the sintered and quenched LRMO material exhibit a uniform distribution of Mn and Ni atoms throughout the crystalline particles such that there are no regions that are Ni rich or Mn rich when imaged by high-angle annular dark-field (HAADF) energy dispersive X-ray spectrometry (EDS) (i.e., in EDS elemental maps of HAADF tunneling electron microscopy images). In one embodiment, the term “no regions that are Ni rich or Mn rich” in a crystalline particle means that there are no crystalline volumes greater than 3 × 3 × 3 nm in the crystalline particle in which there is a greater than 3% difference between ratios of Ni and Mn atoms compared to average ratios of the Ni and Mn atoms in the entire crystalline particle.
The crystal structure of the as-formed active LRMO material may be changed by electrochemical cycling. For example, when the active LRMO material is included as an active material in an electrochemical cell, after a first charge/discharge cycle, the monoclinic phase may no longer be present at detectable levels. It is believed that the monoclinic phase may be consumed during Li ion insertion and/or extraction.
LRMO materials may be formed from various precursor materials. For example, precursor materials may be metalloorganic compounds comprising a metal, such as Li, Mn, and/or Ni, and a solubilizing agent, such as an organic ligand. For example, precursor materials may include metal acetates, metal carbonates, metal nitrates, metal sulfates, and/or metal hydroxides.
In various embodiments, LRMO materials may be formed by thermally decomposing a precursor material followed by sintering and quenching the resulting thermally decomposed LRMO material. The precursor material may comprise a gel formed via a sol-gel process. The present inventors have determined that rapidly decomposing a precursor material gel may improve the homogeneity of LRMO materials. For example, in a sol part of the sol—gel process, stoichiometric amounts of Li, Mn, and Ni-containing precursors may be mixed with water to form an aqueous mixture. For example, stoichiometric amounts of Li(CH3COO)*2H2O, Mn(CH3COO)2*4H2O, and Ni(NO3)2*6H2O, may be mixed to form the aqueous mixture. However, the present disclosure is not limited to any particular precursor materials. For example, in some embodiments, all acetate precursors or all nitrate precursors (i.e., lithium, manganese and nickel nitrates) may be used. In some embodiments, the mixture may comprise from a 0.01 to 0.20 molar fractional excess of the lithium acetate precursor to compensate for lithium loss during processing.
The mixture may then be heated to form the precursor gel. For example, the mixture may be heated at a temperature ranging from about 90° C. to about 150° C., such as about 100° C., for a time period sufficient for gelation to occur.
The gel may then be thermally decomposed. For example, the gel may be heated at a temperature and for a time period sufficient to extract (e.g., volatize and/or decompose) solubilizing agents, such as organic ligands and/or solvents of the gel and form a thermally decomposed LRMO material.
The thermal decomposition may be performed using a conventional furnace, such as a muffle box and/or tube furnace. However, such devices generally have slow heating and cooling rates on the order of 1 to 10° C. per minute, and do not employ any type of direct radiation thermal energy input. As such, conventional furnaces may require at least 8 hours of processing time and a significant amount of energy to form the thermally decomposed LRMO material.
According to various embodiments, rapid (e.g., high rate) heating methods are used to form a thermally decomposed LRMO material. For example, an embodiment may utilize microwave radiation to thermally process LRMO precursor materials (i.e., to rapidly decompose LRMO precursors, such as the gel precursors formed via a sol-gel process).
Microwaves are defined as electromagnetic radiation with wavelengths from 1 mm to 1 m. The widely adopted domestic microwave ovens use microwave radiation with frequency around 2.45 GHz. Regulations have restricted the microwave frequencies that may be used for domestic and industrial applications. The mechanisms of microwave heating are attributed into two categories: 1) the flow of current under the external electric field generated by microwave radiation generates heat due to ohmic effect; and 2) dipoles that exist in ceramic re-orientate themselves under a changing electric field generate heat due to frictions.
Microwave heating may allow for lower thermal processing (e.g., precursor thermal decomposition) temperatures. Microwave heating may also allow for shorter heating times, due to very rapid local heating, as compared to conventional furnace heating processes. The intimate mixing of precursor materials may also allow for more efficient volumetric heating than conventional furnace heating processes.
In some embodiments, microwave heating is used to heat and decompose precursor materials and form thermally decomposed LRMO materials. For example, the precursor materials may include ligands and/or metals that are highly susceptible to microwave radiation. As such, various embodiments utilize microwave radiation in order to heat precursors and/or precursor gels to very high temperatures in very short periods of time. It has also been found that microwave heating also provides highly uniform heat dispersion. As such, employing microwave radiation can dramatically change the rate of heating and the resulting thermally decomposed LRMO material organization and/or structure. For example, microwave heating of a precursor gel may result in a highly homogenous thermally decomposed LRMO material. The thermally decomposed LRMO material may be in a form of an inorganic ash that is devoid of organic components (e.g., contains no carbon or an unavoidable amount of carbon). As such, microwave heating may allow for thermally decomposed LRMO materials to be formed without the need for a separate furnace firing, which may be omitted.
For example, a precursor gel may be provided to a microwave furnace, where microwave radiation is used to decompose the gel and form the thermally decomposed LRMO material. For example, microwave radiation may be used to heat the gel to a temperature of at least 350° C., such as a temperature ranging from about 350° C. to about 500° C., for a time period sufficient to volatilize the ligands and/or solvents of the gel and form the thermally decomposed LRMO material (e.g., LRMO inorganic ash). In various embodiments, the thermally decomposed LRMO material may be formed in about 30 minutes or less, such as in about 15 to 30 minutes, using a continuous or pulsed microwave having power level of 20,000 W per kg of microwaved material, or less. Accordingly, the microwave-based heating process may be configured to rapidly remove (e.g., vaporize and/or combust) organic components from precursor species in order to form the thermally decomposed LRMO material having improved structural characteristics, such as homogenous cation and/or metal oxide distribution.
While microwave thermal decomposition of precursor gel formed by the sol-gel process is described above, in other embodiments, the precursors that are thermally decomposed by microwaves may be formed by other methods. For example, alternative precursor preparation methods may include a mechanical milling/mixing method, a freeze-drying rotary evaporation, or a co-precipitation method. In one embodiment co-precipitation method, precursors comprising hydroxides of Mn and Ni may be mixed with lithium carbonate and co-precipitated. For example, solid state precursor materials including Li2CO3 or LiOH, nickel oxide, and manganese oxide may also be used. Such solid state precursors may also have an excess of Li-containing precursor (e.g., lithium carbonate or hydroxide) of 0.01 to 0.20 molar fractional excess to overcome losses in lithium content during processing. The precursors prepared by any of these methods may also be subjected to the microwave thermal decomposition to form the thermally decomposed LRMO material (i.e., the LRMO inorganic ash).
The thermally decomposed LRMO material (i.e., the LRMO inorganic ash) may then be mixed and ground (e.g., milled) to form a precursor LRMO powder. The precursor LRMO powder is then thermally processed (e.g., sintered) in any suitable thermal processing apparatus, such as in a furnace, such as a tube furnace, muffle box, etc., to form a sintered LRMO material. For example, the precursor LRMO powder material may be heated (e.g., sintered) at the thermal processing temperature (e.g., a temperature of at least 800° C., such as about 900° C.), for a time period ranging from about 12 to about 24 hours, and then the sintered LRMO material may be rapidly or ultra-rapidly quenched as described above to form the quenched LRMO material. The quenched LRMO material may then be dried and optionally reground (e.g., milled) into a LRMO active material (e.g., active cathode material powder). This LRMO active cathode material powder may then be mixed with a binder or other inactive cathode material to form a cathode of a Li-ion battery.
According to various embodiments, methods of forming LRMO materials may include a combination of rapid heating, such as microwave heating, for at least a part of the thermal processing, combined with rapid or ultra-rapid quenching, in order to produce LRMO materials having unexpectedly high performance. Specifically, this process may produce LRMO material having a high degree of atom/cation disorder/homogeneity (which can be quantified using X-ray diffraction), along with no or substantially no surface segregation of nickel or nickel oxide in the particles (e.g., crystallites), which can be observed using transmission electron microscopy. The combination of these material attributes produces cathode active materials that exhibit little to no capacity fade over 100′s to 1000′s of charge/discharge cycles, a substantially reduced or eliminated loss in average discharge voltage during cycling, and rate capabilities that are suitable for commercial use.
According to various embodiments, the embodiment methods which include microwave heating and/or rapid/ultra-rapid quenching step, may be used to form LRMO active materials that do not suffer from the chemical instability of prior art LRMO materials. In particular, the rapid or ultra-rapid quenching step may be used to form LRMO active materials having reduced Ni surface segregation and increased structural homogeneity, as compared to conventional LRMO materials which are slow cooled after sintering. In various embodiments, the above microwave heating process may be used in conjunction with rapid or ultra-rapid quenching to form LRMO active materials. For example, thermally decomposed LRMO materials formed using microwave decomposition may be sintered and then subjected to the rapid or ultra-rapid quenching process.
In one embodiment, a cathode electrode (i.e., positive electrode) includes a LRMO active material comprising a powder embedded in a binder. The powder may have an average particle / agglomerate size ranging from about 0.1 µm to about 10 µm and am average crystal (i.e., crystallite) size ranging from about 25 nm to about 500 nm. In one embodiment, the particles of the LRMO active material powder may have at least one of a spinel surface layer, a carbon coating (e.g., resulting from the carbohydrate additive in the quench bath) and/or passivated oxygen bonds on a surface (e.g., resulting from the acid additive in the quench bath). The cathode electrode may be included in a battery, such as a lithium-ion battery, that also includes an anode electrode (i.e., a negative electrode), an electrolyte and a separator.
In one embodiment, the cathode electrode active material may be represented by a chemical formula Lix(MnyNi1-y)2-xO2, where x is greater than 1.05 and less than 1.25, and y ranges from 0.95 to 0.1. The active material may comprise layered hexagonal (e.g., rhombohedral) and monoclinic phases at least prior to first electrochemically cycling a battery containing the cathode electrode. The active material may exhibit at least one of (i) a (106)+(102):(101) x-ray diffraction peak intensity ratio of greater than 0.32, such as 0.33 to 0.346; and/or (ii), a (003) to (104) x-ray diffraction peak ratio of greater than 2, such as 2.01 to 2.575; and/or (iii) delivery of at least 200 mAh/g, such as 200 to 230 mAh/g, specific capacity on first discharge (e.g., at C/2 rate) when the cathode electrode is included in a lithium-ion battery; and/or (iv) the lithium-ion battery exhibits less than 10% loss in average discharge voltage at a C/20 rate after 100 charge/discharge cycles when the cathode electrode is included in the lithium-ion battery; and/or (v) less than 10%, such as less than 5% capacity fade (e.g., 0 to 4% capacity fade or an increase in capacity) over at least 100 charge/discharge cycles, such as over 200 C/5 charge/discharge cycles, when included in the positive electrode of the lithium-ion battery. In one embodiment, the lithium-ion battery may include lithium or graphite as the anode electrode.
In one embodiment, an average discharge voltage of the battery (e.g., lithium-ion battery) does not decrease more than 5% (e.g., 0 to 4%) over 50 C/20 (charge) - C/2 (discharge) charge/discharge cycles; and/or a discharge capacity of the battery is greater than 80% of its original capacity after 800 C/20-C/2 charge/discharge cycles.
A LRMO powder having the formula Lix(MnyNi1-y)2-xO2, where x = 1.16 and y = 0.7 was produced using the following method. In particular, a precursor material gel was produced using a sol-gel solid-state synthesis method. Synthesis of the sol included forming an aqueous mixture including stoichiometric amounts of Li(CH3COO)*2H2O, Mn(CH3COO)2*4H2O, and Ni(NO3)2*6H2O. The mixture was heated at 100° C. until the gel was formed. The gel was poured into an alumina crucible and then fired at 400° C. for 90 minutes, resulting in an ash devoid of organics. The resultant ash was ground and re-fired in the crucible at 500° C. for 3 hours and then allowed to naturally cool before being reground, after which the powder was sintered at 900° C. for 24 hours before being quenched. All sintering happened in a box furnace in ambient fume hood conditions. All quenching took place after 12 - 24 hours of heating at 900° C.
Referring to
In a first comparative example, the LRMO material was allowed to slowly cool in the furnace 110 after the sintering at 900° C. In a second comparative example, the LRMO material was cooled by being dumped onto a metal plate after the sintering. In a third comparative example, the LRMO material was first cooled to room temperature slowly and then inserted into tube furnace 110 for the ultra-rapid quench step, which was kept at 900° C. for 30 to 120 minutes prior to the ultra-rapid quench step.
In alternative examples, LRMO power was formed using a rapid precursor decomposition process. In particular, the sol-gel precursor material described above was decomposed using microwave radiation to form an LRMO powder having improved component distribution. In particular, the application of microwave radiation resulted in rapid volatilization of the organic components of the precursor materials, due to the absorption of microwave energy by the organic components. As such, the LRMO components were homogeneously mixed on a molecular level due to the thermal energy generated by the microwave radiation. The resulting LRMO powder was then sintered for between 12 and 24 hours at 900° C. and then ultra-rapidly quenched as described above.
Multiple larger batches (up to 1 kg) of the cathode material were produced both with and without microwave decomposition and ultra-rapid quenching.
An assessment of the XRD patterns shows that the LRMO materials possess the expected hexagonal (e.g., rhombohedral) phase LiNiO2-related, space group (R-3m) and a monoclinic phase (Li2NiO3-related, space group (C2/c).
One method to assess the degree of metal cation disorder in the materials is to use the ratio of peak intensities in the x-ray diffraction patterns. Specifically, the ratio of the intensity of the (003) peak to the (104) peak is commonly known as rough measurement of electrochemical activity in mixed cation materials with this predominately layered crystal structure, while the ratio of the sum of the intensities of (006) and (102) peaks to the intensity of the (101) peak is an indicator of cation disorder. Based on this, the material that has been both microwave-processed during the decomposition stage and then ultra-rapidly quenched offers significantly higher indications of electrochemical activity and lower degree of cation order (and therefore a higher degree of cation disorder) than slow cooled material.
Table 2 shows XRD peak intensity ratios for a comparative example LRMO material subjected to a slow quench after sintering (row 1), and for an exemplary LRMO material made subjected to the ultra-rapid quench after sintering (row 2). Both materials have formula Lix(MnyNi1-y)2-xO2 where x = 1.2, and y = 0.75. Importantly, the exemplary ultra-rapidly quenched material exhibits XRD characteristics that show an increase in atomic disordering in the material that have significantly higher electrochemical activity and more cation disorder/metal oxide homogeneity than the comparative example material. Specifically, the exemplary material shows an increase in the ratio of the sum of the intensities of (006) and (102) peaks to the intensity of the (101) peak, in this case of about 9%. This significant increase in cation disorder represents a situation where the Ni and Mn atoms are more completely mixed (and are therefore not grouped) in the material. For this reason, such exemplary material may be referred to as “cation-disordered lithium-rich lithium manganese nickel oxide”, and these data demonstrate that different states of matter can be created based on the processing conditions used, and in particular, the rate of cooling used.
Synthesized cathode materials were mixed with Super-P carbon black and polyvinylidene fluoride (PVDF) in a ratio of 8:1.2:0.8 making the active material 80% of the overall mass. The resultant blend was then mixed into ~15 ml of N-Methyl-2-Pyrrolidone for a minimum of one hour before two 10-minute sonication steps, after which the resultant slurry was further allowed to mix on a hot plate at 100° C. for a minimum of 30 minutes before being spray coated onto 10×10 cm, 10 µm thick aluminum foil heated above 100° C. Foil was allowed to dry in a 70° C. oven in air over night before being punched out with a biopsy punch. These punches were then used to make 2032 coin cells that used lithium foil as the anode, 1.0 M LiPF6 50/50 ethylene carbonate/dimethyl carbonate solution as the electrolyte, a Celgard battery separator, 0.5 mm stainless steel spacers, and wave springs on the cathode side to ensure mechanical contact within the cell; each coin cell was assembled and sealed through use of a coin cell press in a dry low oxygen argon atmosphere.
The electrochemical performance investigations used low-current Neware or bio-logic battery testers to conduct potential limited galvanostatic testing with constant current on the coin cells made in the process described above. The cells were cycled using constant current charge/discharge conditions at rates ranging from C/20 to C/2 between 4.8 and 2 V.
Referring to
In contrast to the comparative exemplary material shown in
Both comparative and exemplary cells were cycled twice with both charge and discharge currents at a rate of approximately C/20 to condition the cathode material. Subsequent to this, 25 cycles were performed with charge rates of C/20 and discharge rates of C/2. This set of 27 cycles is referred to as a round of cycling, and all cells experienced this regime twice. As can be seen from
Thus, as shown in
Synthesized LRMO active material (i.e., the sintered and quenched loose powder) was mixed with Super-P carbon black and polyvinylidene fluoride (PVDF) in a ratio of 8:1.2:0.8 making the active LRMO 80% of the overall mass. The resultant blend was then mixed into about 15 ml of N-methyl-2-pyrrolidone, for a minimum of one hour. Two 10-minute sonication steps were then performed, after which the resultant slurry was further allowed to mix on a hot plate at 100° C., for a minimum of 30 minutes, before being spray-coated onto 10 × 10 cm, 10 µm thick aluminum foil heated above 100° C. The foil was allowed to dry in a 70° C. oven in air over night before being sampled into round electrode discs. The resultant punches were then used to make 2032-type coin cells that included lithium foil anodes, 1.0 M LiPF6 50/50 ethylene carbonate/dimethyl carbonate solution as the electrolyte, a Celgard battery separator, 0.5 mm stainless steel spacers, and wave springs on the cathode side to ensure mechanical contact within the cell. Each coin cell was assembled and sealed through use of a coin cell press in a dry low oxygen argon atmosphere.
A LAND battery tester was used to conduct potential limited galvanostatic testing with constant current on the coin cells made in the process described above. A minimum of three cells, per variant, were cycled at ambient temperatures between 2.0 V and 4.8 V. Cells were cycled twice with both charge and discharge currents at a rate of approximately C/20 to condition the cathode material. The cells were then charged and discharged for 25 cycles at a C/20 charge rate and a C/2 discharge rate. These 27 cycles may be referred to as a round of cycling, and all cells experienced two rounds of cycling.
The following Table III shows the discharge capacities (DC) of the samples over the course of cycling, along with the C/20:C/2 ratio of DC28/DC27. Rate ability was accessed by taking the ratio of a C/20 discharge capacity and a C/2 discharge capacity, such the discharge capacities of the 27th and 28th cycles. Note discharge cycles 1, 2, and 28 were at a C/20 rate, while discharge cycles 3, 27, and 54 were at a C/2 rate.
Referring to
The initial capacity of 25Hq had the highest initial capacity of the x = 0.25 samples with 186 mAh g-1 and 25Mq has the lowest with 127 mAh g-1. As seen in Table III, all x = 0.25 samples saw improved capacities over the course of cycling, except for the 25Mq sample. 25Hq saw the largest capacity increase of all three samples. The 25Mq sample also displays severe voltage decay with the voltage dropping below 3 V over the course of cycling. While the 25Hq and 25Lq samples also had inflection points on their discharge curves at 2.8 V, theirs do not display such a severe voltage fade. The voltage decay was not seen in the C/20 discharges of the 25Hq and 25Lq samples, however the 25Mq sample’s C/20 discharges experienced voltage decay. The average discharge voltage of the 0.25 samples reflects these voltage fades with 25Mq having the lowest average voltage over the course of cycling, and 25Lq having slightly higher average discharge voltages than 25Hq.
With regard to rate capability, as seen in Table III, the C/20:C/2 ratios for 25Hq, 25Lq, and 25Mq samples are 1.19, 1.25, and 1.39, respectively.
Referring to
The capacity of all x = 0.17 samples increased between the first two C/20 discharges by roughly 10 mAh g-1. As seen in Table III, the second round of C/20 discharges saw capacity increases of 31%, 73% and 91% for 17Hq, 17Lq, and 17Mq, respectively. There was near uniform voltage decay behavior for all three samples and average plateau voltages fell around 0.4 V over the course the cycling. However, the voltage decay was not seen in these samples’ C/20 discharge curves. The x = 0.17 samples also have similar average discharge voltages over time. The main difference is how over the first round of cycling the 17Mq’s average voltage increases, but by the 2nd round of cycling it matches the voltage fade tend of 17Hq and 17Lq.
Referring to
As seen in Table III, all of the x = 0.10 samples experienced initial capacity increases during the first C/20 cycles on the order of 5 mAh g-1, followed by 300%, 60% and 67% improvement in capacity on the second round of C/20 discharges for 10Hq, 10Lq, and 10Mq samples, respectively. By the end of the first round of C/2 discharging, the capacities of all x = 0.10 samples exceeded or caught up to the initial C/20 capacities. Over the course of the 2 rounds of C/2 discharging, 10Hq saw capacity increases of 197% and 50%, 10Lq saw capacity increases of 25% and 16%, and 10Mq saw increases of 36% and 20%, over the course of the first and second rounds respectively. The discharge plateau of the 10Lq and 10Mq samples started at ~3.0 V while the plateau for the 10Hq sample started at 3.2 V; the voltage behavior of 10Hq of the course of cycling was different than 10Lq and 10Mq. The voltage behaviors of all the x = 0.10 samples were rate dependent, and the average discharge voltage of all three samples’ C/20 discharges increased over the course of cycling. However, the 10Lq and 10Mq samples’ C/2 discharges showed signs of voltage decay, while 10Hq’s did not.
Additionally, the 10Lq and 10Mq samples had an inflection point at 2.2 V that is only present on the C/20 discharge curves. These voltage behaviors of the x = 0.10 samples showed average discharge voltages of the 10Lq and 10Mq samples are higher than 10Hq’s, but also display a greater degree of voltage fade.
With regard to rate capability, as shown in Table III, the 10Hq, 10Lq, and 10Mq samples C/20:C/2 ratios of 1.27, 1.60, and 1.67, respectively. It is noted that the effective charge and discharge for each cycle also evolves significantly with cycling, which makes the DC28/DC27 ratio for 10Hq effectively a C/10:C/1 ratio.
Varied phase transformation over the course of testing was manifested in the voltage profiles observed during cycling. The expected voltage plateaus seen in the x = 0.25 samples suggest that the expected classical phase transformation occurred.
Referring to
The 10Mq sample had substantially different crystal structure after cycle testing, though both 10Mq and 10Lq samples still had some visible peaks at 22°, further suggesting that the electrochemical phase transformations seen in
Referring to
Both nickel content and quench method influence the structure, and electrochemical behavior of LRMO cathodes. In general, the materials had higher capacities and more classical voltage behavior when synthesized with a higher Ni content and/or a more rapid quench rate, though the outcomes were sometimes nuanced.
The XRD patterns of LRMO powders showed structural dependence on both nickel content and quench method. Slight crystallographic variation across samples of various nickel contents was expected and was observed between the x = 0.25 and x = 0.17 and 10Hq samples. The XRD patterns of 10Lq and 10Mq have a large number of secondary peaks while 10Hq’s XRD pattern does not. The secondary peaks seen in the patterns of 10Lq and 10Mq are consistent with the secondary peaks seen in the 25Mq and 17Mq samples’ XRD patterns. These examples suggest that quench rate is important in determining structure, phase content, and phase purity.
The secondary layered phase found in many samples may be the result of localized relatively nickel-rich heterogeneities with the corresponding larger lattice parameters. The (110) peak splitting is present in all samples’ XRD patterns except 25Hq and 25Lq’s, which demonstrates that slower quenching gives rise to nickel heterogeneity. The 25Mq and 17Mq samples’ XRD patterns have additional secondary peaks at (101), (104), (107) which are seen in the 10Lq and 10Mq samples. Though it must be noted that the (104) secondary peaks for 25Mq and 10Lq likely arise from contaminates. These additional peaks, while varied, appear for all metal quenched samples, which demonstrates how structure depends on both nickel content and quenching. These data support the concept that slower quench methods giving rise to segregated nickel-rich phase regions, as well as the formation of contaminates in the material, thus determining the localized ordering of nickel in the samples regardless of Ni content.
Since Ni2+ ions have a greater ionic radius than Mn ions, it is believed that with less Ni present, there are fewer instances of local lattice expansion. Samples with higher nickel content should have higher degrees of long-range ordering distributing the nickel ions, with more favorable orderings resulting in smaller lattice parameters. Rapidly quenching these sample preserves long-range ordering and smaller lattice parameters, while slower quenching would allow for the nucleation of contaminates and the evolution of nickel heterogeneities, both of which would distort the average lattice parameter. The cross over point seen in
The samples’ electrochemical behavior was affected by both the nickel content as well as the quench method. The first charge behavior of the material is indicative of purity and capacity, as higher performance materials are known to exhibit a single strong plateau consistent with a phase transition via nickel-catalyzed oxygen and lithium loss.
Referring to
The presence of inflection points on non-water quenched samples, besides some on 10Hq, provides further evidence that these inflection points are related to phase heterogeneity. The 10Hq sample starts with these inflection points, but by the 54th cycle its charge profile more closely resembles the x = 0.17 samples than the x = 0.10 samples it originally resembled. These data are thus consistent with the evolution of nickel heterogeneities prolonging the 4.5 V phase transition.
Discharge profiles of the samples also show cycling behavior over time is influenced by nickel composition and quench method. Referring to
Voltage decay in 25Hq and 25Lq is minor when compared to x = 0.17 samples’ voltage decay, their associated voltage plateaus are also at different voltages. The more minor 25Hq and 25Lq voltage decay is mostly consistent with a phase transformation to a spinel-like phase over the course of cycling, which is associated with a 3 V plateau. The more severe voltage decay of the x = 0.17 samples is also mostly consistent with a phase transformation to a spinel-like phase. In both cases, but particularly the case of x = 0.17 samples, the voltage plateaus are close to the average voltage of the Ni2+/3+/4+ redox in manganese rich environments, suggesting that these plateaus are driven by nickel redox, and thus nickel distribution. This loss of voltage and nickel redistribution is mostly consistent with the evolution of the spinel-like phase, with the main inconsistency is the increase in capacity, while evolution of spinel-like phases has been associated with both initial capacity gains and losses it seems to universally be associated with significant structural degradation. Therefore, the voltage decay of the structurally robust 25Hq, 25Lq and x = 0.17 samples is likely not entirely due to the evolution of a spinel-like phase.
The evolution of a spinel-like phase also does not account for the differences in behavior between discharge rates, particularly with x = 0.10 samples. The C/20 discharges of the x = 0.10 samples start at a voltage resembling a decayed sample and over the course of cycling their voltage increase; the C/2 discharges of x = 0.10 samples experienced some degree of voltage fade. While the lower initial potential of the samples is likely do to their greater manganese concentration and subsequent lower potential of the nickel redox, the inconsistent voltage behavior cannot be entirely accounted for by the formation of spinel-like phase, especially when considering their rapid increases in capacity. By contrast 25Mq’s lower manganese concentration, capacity loss, and more rapid voltage decay indicate formation of spinel-like phase. These factors, practically how its discharge voltage plateau starts at 3 V, are consistent with the voltage-decay mechanism of spinel-like phase evolution. It is possible that the phase impurities evolved during a slow quench could have left 25Mq more susceptible to the evolution of the spinel-like phase. The voltage plateaus of 25Mq fall within the range of the Mn3+/4+ redox couple, and it would be possible for the manganese and nickel to form hybrid redox couples which could also account for the voltage decay. 10Lq and 10Mq’s discharge plateaus, similarly to 25Mq start at 3 V, which suggests these samples might also be experiencing some degree of transformation to a spinel-like phase. The XRD of all samples, besides 10Mq, have peaks that are indicative of the R-3m layered structure, further suggesting that the evolution of a spinel-like phase is not entirely responsible for the voltage fade or the changes in capacity.
The electrochemical cycling data of the LRMO cathodes saw consistent increases in capacity, except for 25Mq. While x = 0.25 samples saw minor gains in capacity the x = 0.17 samples saw more significant increases, and the x = 0.10 samples saw even more. The increase in percentage of specific capacity over cycling therefore exhibited an inverse relationship to nickel content regardless of quench method. The greatest increases in capacity were seen in the 10Hq sample and then the 10Mq and 10Lq samples. Since impurities are linked to nickel heterogeneity, this relationship suggests that the capacity increases are at least partially driven by the nickel content homogenizing over the course of cycling via an “electrochemical annealing” process.
The comparative XRD of the post cycling cathode material to pristine cathode materials shows very similar behaviors across all samples besides 10Lq and 10Mq, with transition metal superlattice peaks disappearing after cycling. 10Lq has some preserved superlattice peaks post cycling, and the 10Mq sample sees the emergence of several new peaks, marking a significant difference between the two samples. This difference further shows the importance of quench rate, as there appears to be a synthetic lower limit for LRMO, where 0.17 > x > 0.10, under slower quenching conditions. However, the 10Hq sample’s behavior is different and shows that more rapid quenching of the sample can result in stability and long-term performance associated with higher Ni content samples.
Electrochemical testing of these materials show that the fast quench material has excellent capacity and capacity retention and is the only variant to exhibit an increase in capacity during cycling. After 50 full charge/discharge cycles, this material yields specific capacity of nearly 230 mAh/g at a C/2 rate, which is far better than materials that were cooled in other ways.
The finding that extremely rapid cooling of this class of materials during synthesis using immersion in water results in material with superior and differentiated crystal structure as well as never reported electrochemical behavior. Specifically, we find that this water quenched material: (a) showed a significant increase in capacity over 50 cycles, (b) did not exhibit the commonly reported voltage fade (wherein the average discharge voltage of the cell decreases significantly over use), (c) has a specific capacity that exceeds 250 mAh/g after 25 cycles at a C/2 rate and 4 cycles at a C/2 rate, and (d) has a specific capacity exceeds 230 mAh/g (e.g., 231 to 240 mAg/g) after 50 cycles at the C/2 rate with less than 10% loss in average voltage during discharge (e.g., as shown in
As shown in
There were also superlattice peaks around 22° which are indicative of this family of compounds. The XRD patterns of the 10Lq and 10Mq samples also had significant peaks to the left of their (101), (104), (015), (107), and (108) peaks, suggesting the presence of phase impurities with similar structure and a larger lattice parameter than the bulk phase. The lack of other peaks suggest that, in this case, all impurities are isostructural with the bulk phase of the material. The XRD pattern of the 10Hq sample showed only small additional (107), (108), and (110) peaks. While not as visible the XRD patterns, the 17Mq and 25Mq samples also had indications of phase impurities; there are small secondary peaks to the left of the (104) and their (107) peaks, respectively. In addition, the (108) peak of the 25Mq sample had a shoulder to its left. Closer examination of the (104) maxima indicated the difference between this secondary set of peaks, with the secondary peaks of 25Hq and 10Mq samples, suggest that the isostructural impurities are likely a nickel rich layered structure, while the peaks for the 10Lq and 25Mq samples suggest the isostructural impurities are likely ordered rock salt. These data indicate that there should be two sources for these peak sets: one being the additional layered phase and the other being contaminate rock salt. Herein, “secondary layered phase” will refer to local regions with compositional variance and corresponding structural distortions, specifically areas with higher nickel content and the resultant larger lattice parameter, while “contaminates” will refer to the rock salt phases.
The lattice parameters of the powders in
In one embodiment, a method of forming an active material for a positive electrode of a lithium-ion battery comprises quenching a powder of the active material in water. In one embodiment, the method further comprises firing the active material powder prior to the quenching. The active material may be fired at a temperature of at least 800° C. The water may be at room temperature prior to the quenching, and the powder of the active material may be quenched at a rate of least 1750° C./second.
In one embodiment, the active material comprises layered lithium-rich nickel manganese oxide. The excess Li, Ni and Mn atoms may be homogeneously and uniformly distributed throughout transition metal crystal lattice sites, such that there are no crystalline volumes greater than 3 × 3 × 3 nm in the material in which there is a greater than 3% difference between ratios of Ni, Mn and Li atoms compared to average ratios of the Ni, Mn and Li atoms of a bulk material. Particles of the powder of the active material may be in a shape of agglomerates which have an average size ranging from about 0.1 µm to about 20 µm, and the agglomerates of the powder of the active material are composed of crystallites having an average size ranging from about 25 nm to about 500 nm. The powder of the active material may comprise a composite of hexagonal and monoclinic phases after the quenching, and is a combination of LiMO2 R-3m and Li2MnO3 C2/m phases, where M is at least one of Ni or Mn. The powder of the active material may comprise a solid solution with a crystal structure that predominately or completely possess a C2/m symmetry. The powder of the active material may comprise a solid solution with a crystal structure that predominately or completely possess a R-3m symmetry.
In one embodiment, the active material is represented by a formula: Li[NixLi(⅓-2x/3)Mn(⅔-x/3)]O2 where 0 < x < 0.5. In one embodiment, the active material is substantially free of cobalt; and the active material is represented by the formula: Li[NixLi(⅓-2x/3)Mn(⅔-x/3)]O2 where 0.19 < x < 0.26, or by the formula: Li[MxLi(⅓-2x/3)Mn(⅔-x/3)]O2 where 0.19 < x < 0.26, and where M comprises Ni and at least one of Ti, Fe, Al or Cr.
In one embodiment, the water comprises an additive solvated therein. The water may comprise from 0.01 moles per liter to 1.0 moles per liter of the additive. In one embodiment, additive comprises an acid, which may be selected from sulfuric acid, citric acid, acetic acid, phosphoric acid, hydrochloric acid, ammonium phosphate, or combinations thereof. In another embodiment, the additive comprises a carbohydrate, which may be selected from fructose, galactose glucose, lactose, maltose, sucrose, or a combination thereof.
In one embodiment, the active material is placed into the positive electrode of the lithium-ion battery cell which further comprises a negative electrode and an electrolyte. The active material comprises hexagonal and monoclinic phases prior to the electrochemical cycling of the battery; and the active material powder does not comprise the monoclinic phase after the electrochemical cycling.
In one embodiment, a specific discharge capacity of the battery cell increases by at least 10% over 50 electrochemical cycles at charge rate of C/20 and discharge rate of C/2 in a voltage range of 2 V to 4.8 V at room temperature; and the battery cell has a specific capacity of at least 230 mAh/g after the 50 electrochemical cycles at the discharge rate of C/2.
In one embodiment, a lithium-ion battery cell comprises: a negative electrode; an electrolyte; and a positive electrode comprising a layered lithium rich nickel manganese oxide active material, wherein a specific discharge capacity of the battery cell increases by at least 10% over 50 electrochemical cycles at a charge rate of C/20 and a discharge rate of C/2, and the battery cell has a specific capacity of at least 230 mAh/g after the 50 electrochemical cycles at the discharge rate of C/2.
In one embodiment, the specific discharge capacity of the battery cell increases by at least 10% over two electrochemical cycles at the charge rate of C/20 and the discharge rate of C/20, followed by twenty five electrochemical cycles at the charge rate of C/20 and the discharge rate of C/2, followed by two additional electrochemical cycles at the charge rate of C/20 and the discharge rate of C/20, and followed by twenty five additional electrochemical cycles at the charge rate of C/20 and the discharge rate of C/2 in a voltage range of 2 V to 4.8 V at room temperature. In one embodiment, an average discharge voltage of the battery cell does not decrease more than 10% over the 50 electrochemical cycles at the discharge rate of C/2.
In one embodiment, the active material is represented by a formula: Li[MxLi(⅓-2x/3)Mn(⅔-x/3)]O2 where 0 < x < 0.5, and M comprises Ni or a combination of Ni and at least one of Ni, Al, Fe or Cr. In one embodiment, the active material is substantially free of cobalt; and the active material is represented by the formula: Li[MxLi(⅓-2x/3)Mn(⅔-x/3)]O2 where 0.19 < x < 0.26 and M comprises Ni. In one embodiment, the active material is represented by a formula y(LiMO2)·(1-y)LiMnO3, where y ranges between 0.8 and 1, and M comprises at least Ni and Mn.
In one embodiment, particles of the powder of the active material are in a shape of agglomerates which have an average size ranging from about 0.1 µm to about 10 µm, and the agglomerates of the powder of the active material are composed of crystallites having an average crystal size ranging from about 25 nm to about 500 nm; and particles of the active material powder have at least one of a spinel surface layer, a carbon coating or passivated oxygen bonds on a surface.
In one embodiment, excess Li, Ni and Mn atoms are homogeneously and uniformly distributed throughout transition metal crystal lattice sites, such that there are no crystalline volumes greater than 3 × 3 × 3 nm in the material in which there is a greater than 3% difference between ratios of Ni, Mn and Li atoms compared to average ratios of the Ni, Mn and Li atoms of a bulk material.
The preceding description of the disclosed aspects is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these aspects will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other aspects without departing from the scope of the invention. Thus, the present invention is not intended to be limited to the aspects shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
This application is a continuation-in-part of U.S. Pat. Application No. 17/810,722, filed on Jul. 5, 2022, and claims the benefit of priority to U.S. Provisional Pat. Application No. 63/296,243, filed on Jan. 4, 2022, and U.S. Provisional Pat. Application No. 63/296,244, filed on Jan. 4, 2022, the entire contents of which are incorporated herein by reference.
| Number | Date | Country | |
|---|---|---|---|
| 63296243 | Jan 2022 | US | |
| 63296244 | Jan 2022 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 17810722 | Jul 2022 | US |
| Child | 18149475 | US |
