PATENT DOCUMENT

Publication Number: US-10615413-B2
Application Number: US-201414206654-A
Country: US
Kind Code: B2

Title: High voltage, high volumetric energy density li-ion battery using advanced cathode materials

Abstract:
The disclosed embodiments provide a battery cell. The battery cell includes an anode containing an anode current collector and an anode active material disposed over the anode current collector. The battery cell also includes a cathode containing a cathode current collector and a cathode active material disposed over the cathode current collector. The cathode active material has a composition represented by xLi 2 MO 3 ·(1- x )LiCo y M′ (1-y) O 2 .

Claims:
What is claimed is: 
     
       1. A cathode active material composition having a composition represented by xLi 2 MO 3 ·(1-x)LiCo y M′ (1-y) O 2 ;
 wherein 0.01≤x&lt;0.30; 
 wherein M is manganese; 
 wherein 0.8≤y&lt;1.00; 
 wherein M′ is Al. 
 
     
     
       2. A cathode for a battery cell, comprising:
 a cathode current collector; 
 a cathode active material disposed over the cathode current collector, having a composition represented by xLi 2 MO 3 ·(1-x)LiCo y M′ (1-y) O 2 ;
 wherein 0.01≤x&lt;0.30; 
 wherein M is manganese; 
 wherein 0.8≤y&lt;1.00; 
 wherein M′ is Al. 
 
 
     
     
       3. A battery cell, comprising:
 an anode, comprising:
 an anode current collector; and 
 an anode active material disposed over the anode current collector; and 
 
 a cathode, comprising:
 a cathode current collector; 
 a cathode active material disposed over the cathode current collector, having a composition represented by xLi 2 MO 3 ·(1-x)LiCo y M′ (1-y) O 2 ; 
 wherein 0.01≤x&lt;0.30; 
 wherein M is manganese; 
 wherein 0.8≤y&lt;1.00; 
 wherein M′ is Al. 
 
 
     
     
       4. The battery cell of  claim 3 , wherein the composition is formed using at least one of:
 a mixed-metal hydrated hydroxide precursor made using a solution co-precipitation method; and 
 a lithium addition solid-state reaction. 
 
     
     
       5. The battery cell of  claim 3 , wherein the cathode has an amount of lithium that can be reversibly extracted from the cathode active material greater than 60%, and a reversible capacity greater than 165 mAh/g. 
     
     
       6. The battery cell of  claim 3 , wherein the cathode has an amount of lithium that can be reversibly extracted from the cathode active material greater than 75%, and a reversible capacity greater than 200 mAh/g. 
     
     
       7. A portable electronic device, comprising:
 a set of components powered by a battery pack; and 
 the battery pack, comprising:
 a battery cell, comprising:
 an anode, comprising:
 an anode current collector; and 
 an anode active material disposed over the anode current collector; and 
 
 a cathode, comprising:
 cathode current collector; 
 a cathode active material disposed over the cathode current collector, comprising a composition represented by xLi 2 MO 3 ·(1-x)LiCo y M′ (1-y) O 2 ; 
 
 
 wherein 0.01≤x&lt;0.30; 
 wherein M is manganese; 
 wherein 0.8≤y&lt;1.00; 
 wherein M′ is Al.

Description:
RELATED APPLICATION 
     This application claims the benefit of U.S. Provisional Application No. 61/777,510, entitled “High Voltage, High Volumetric Density Li-Ion Battery Using Advanced Cathode Materials,” by inventor Hongli Dai, filed 12 Mar. 2013, which is hereby incorporated by reference. 
    
    
     U.S. GOVERNMENT LICENSE RIGHTS 
     This invention was made with U.S. government support under WFO Proposal No. 85F59. The U.S. government has certain rights in the invention. 
    
    
     BACKGROUND 
     Field 
     The present embodiments generally relate to rechargeable batteries. More specifically, the present embodiments relate to the design of a high voltage, high volumetric energy density lithium-ion battery using advanced cathode materials. 
     Related Art 
     Rechargeable batteries are widely used for energy storage in a variety of consumer, medical, aerospace, defense, and/or transportation applications. The most commonly used type of rechargeable battery is a lithium battery, which can include a lithium-ion or a lithium-polymer battery. As battery-powered devices become increasingly small and more powerful, batteries powering these devices need to store more energy in a smaller volume. Consequently, use of battery-powered devices may be facilitated by mechanisms for improving the volumetric energy densities of batteries in the devices. 
     SUMMARY 
     The disclosed embodiments provide a battery cell. The battery cell includes an anode containing an anode current collector and an anode active material disposed over the anode current collector. The battery cell also includes a cathode containing a cathode current collector and a cathode active material disposed over the cathode current collector. The cathode active material has a composition represented by xLi 2 MO 3 ·(1-x)LiCo y M′ (1-y) O 2 . 
     In some embodiments, M is at least one of manganese, titanium, ruthenium, and zirconium. 
     In some embodiments, y=1.00, M′ is not present, and the composition is xLi 2 MO 3 ·(1-x)LiCoO 2 . 
     In some embodiments, 0.5≤y&lt;1.00 and M′ is at least one of a monovalent cation, a divalent cation, a trivalent cation, a tetravalent cation, and a ruthenium cation. 
     In some embodiments, M or M′ contains a mixture of metal cations. 
     In some embodiments, the stoichiometric numbers of the metal cations in the mixture are not equal. 
     In some embodiments, 0.01≤x≤0.50. 
     In some embodiments, the composition is formed using at least one of a mixed-metal hydrated hydroxide precursor made using a solution co-precipitation method and a lithium addition solid-state reaction. 
     In some embodiments, y=1.00, M is Manganese (Mn), and the composition is xLi 2 MnO 3 ·(1-x)LiCoO 2 . 
     In some embodiments, the amount of lithium that can be reversibly extracted from the cathode active material is greater than 165 mAh/g. 
     In some embodiments, the amount of lithium that can be reversibly extracted from the cathode active material is greater than 200 mAh/g. 
    
    
     
       BRIEF DESCRIPTION OF THE FIGURES 
       The patent or application file contains at least one drawing executed in color. Copies of this patent or patent application publication with color drawing(s) will be provided by the Office upon request and payment of the necessary fee. 
         FIG. 1  shows a top-down view of a battery cell in accordance with the disclosed embodiments. 
         FIG. 2  shows a set of layers for a battery cell in accordance with the disclosed embodiments. 
         FIG. 3  shows a scanning electron micrograph (SEM) of a cathode active material composition in accordance with the disclosed embodiments. 
         FIG. 4  shows an X-ray powder diffraction (XRD) of a cathode active material composition in accordance with the disclosed embodiments. 
         FIG. 5  shows a Raman vibrational spectrum of a cathode active material composition in accordance with the disclosed embodiments. 
         FIG. 6  shows an SEM of a cathode active material composition in accordance with the disclosed embodiments. 
         FIG. 7  shows a cell voltage profile for a battery cell in accordance with the disclosed embodiments. 
         FIG. 8  shows a plot of capacity versus cycle number for a battery cell in accordance with the disclosed embodiments. 
         FIG. 9  shows XRD patterns of two cathodes in accordance with the disclosed embodiments. 
         FIG. 10A  shows a cell voltage profile for a battery cell in accordance with the disclosed embodiments. 
         FIG. 10B  shows a cell voltage profile for a battery cell in accordance with the disclosed embodiments. 
         FIG. 10C  shows a cell voltage profile for a battery cell in accordance with the disclosed embodiments. 
         FIG. 10D  shows a plot of capacity versus cycle number for a battery cell in accordance with the disclosed embodiments. 
         FIG. 10E  shows a plot of capacity versus cycle number for a battery cell in accordance with the disclosed embodiments. 
         FIG. 10F  shows a plot of capacity versus cycle number for a battery cell in accordance with the disclosed embodiments. 
         FIG. 10G  shows a dO/dV plot for a battery cell in accordance with the disclosed embodiments. 
         FIG. 11  shows an SEM of a cathode active material composition in accordance with the disclosed embodiments. 
         FIG. 12A  shows a cell voltage profile between 2.75V and 4.4V for a battery cell in accordance with the disclosed embodiments. 
         FIG. 12B  shows a cell voltage profile between 2.75V and 4.5V for a battery cell in accordance with the disclosed embodiments. 
         FIG. 12C  shows a cell voltage profile between 2.75V and 4.6V for a battery cell in accordance with the disclosed embodiments. 
         FIG. 12D  shows a plot of capacity versus cycle number during rate study tests (C rates as marked) between 2.75 Vs and 4.4V for a battery cell in accordance with the disclosed embodiments. 
         FIG. 12E  shows a plot of capacity versus cycle number during rate study tests (C rates as marked) between 2.75V and 4.5V for a battery cell in accordance with the disclosed embodiments. 
         FIG. 12F  shows a plot of capacity versus cycle number during rate study tests (C rates as marked) between 2.75V and 4.6V for a battery cell in accordance with the disclosed embodiments. 
         FIG. 12G  shows a plot of capacity versus cycle number during a cycle performance study for a battery cell cycled between 2.75V and 4.5V in accordance with the disclosed embodiments. 
         FIG. 12H  shows a dO/dV plot for a battery cell in accordance with the disclosed embodiments. 
         FIG. 13  shows a portable electronic device in accordance with the disclosed embodiments. 
     
    
    
     In the figures, like reference numerals refer to the same figure elements. 
     DETAILED DESCRIPTION 
     The following description is presented to enable any person skilled in the art to make and use the embodiments, and is provided in the context of a particular application and its requirements. Various modifications to the disclosed embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be applied to other embodiments and applications without departing from the spirit and scope of the present disclosure. Thus, the present invention is not limited to the embodiments shown, but is to be accorded the widest scope consistent with the principles and features disclosed herein. 
     Lithium cathode active materials containing Co and Mn (e.g., LiNi 1/3 Mn 1/3 Co 1/3 O 2  (NMC)) have been synthesized for use in rechargeable batteries, specifically lithium cells and batteries. Typically, battery cells made using these cathode active materials suffer from low volumetric energy density, high-percent capacity irreversibility in the first cycle, capacity degradation over cycling and low rate. The present embodiments target these shortcomings and offer excellent volumetric energy density, cycle life and high rate discharging capability. 
       FIG. 1  shows a top-down view of a battery cell  100  in accordance with an embodiment. Battery cell  100  may correspond to a lithium-ion or lithium-polymer battery cell that is used to power a device used in a consumer, medical, aerospace, defense, and/or transportation application. Battery cell  100  includes a jelly roll  102  containing a number of layers which are wound together, including a cathode with an active coating, a separator, and an anode with an active coating. More specifically, jelly roll  102  may include one strip of cathode material (e.g., aluminum foil coated with a lithium compound) and one strip of anode material (e.g., copper foil coated with carbon) separated by one strip of separator material (e.g., conducting polymer electrolyte). The cathode, anode, and separator layers may then be wound on a mandrel to form a spirally wound structure. Alternatively, the layers may be stacked and/or used to form other types of battery cell structures, such as bi-cell structures. Jelly rolls are well known in the art and will not be described further. 
     During assembly of battery cell  100 , jelly roll  102  is enclosed in a flexible pouch, which is formed by folding a flexible sheet along a fold line  112 . For example, the flexible sheet may be made of aluminum with a polymer film, such as polypropylene. After the flexible sheet is folded, the flexible sheet can be sealed, for example by applying heat along a side seal  110  and along a terrace seal  108 . The flexible pouch may be less than 120 microns thick to improve the packaging efficiency and/or energy density of battery cell  100 . 
     Jelly roll  102  also includes a set of conductive tabs  106  coupled to the cathode and the anode. Conductive tabs  106  may extend through seals in the pouch (for example, formed using sealing tape  104 ) to provide terminals for battery cell  100 . Conductive tabs  106  may then be used to electrically couple battery cell  100  with one or more other battery cells to form a battery pack. For example, the battery pack may be formed by coupling the battery cells in a series, parallel, or series-and-parallel configuration. The coupled cells may be enclosed in a hard case to complete the battery pack, or the coupled cells may be embedded within the enclosure of a portable electronic device, such as a laptop computer, tablet computer, mobile phone, personal digital assistant (PDA), digital camera, and/or portable media player. 
       FIG. 2  shows a set of layers for a battery cell (e.g., battery cell  100  of  FIG. 1 ) in accordance with the disclosed embodiments. The layers may include a cathode current collector  202 , cathode active coating  204 , separator  206 , anode active coating  208 , and anode current collector  210 . Cathode current collector  202  and cathode active coating  204  may form a cathode for the battery cell, and anode current collector  210  and anode active coating  208  may form an anode for the battery cell. The layers may be wound or stacked to create the battery cell. 
     As mentioned above, cathode current collector  202  may be aluminum foil, cathode active coating  204  may be a lithium compound, anode current collector  210  may be copper foil, anode active coating  208  may be carbon, and separator  206  may include a conducting polymer electrolyte. More specifically, cathode active coating  204  may include a cathode active material composition represented by xLi 2 MO 3 ·(1-x)LiCo y M′ (1-y) O 2 . In the composition, x may range from 0.01 to less than 1.00 (0.01≤x≤1.00), and y may range from 0.50 to 1.00 (0.50≤y≤1.00). M may be Mn, Ti, Ru, Zr or a mixture thereof, and M′, if present, may include one or more metal cations selected preferably from one or more monovalent, divalent, trivalent or tetravalent cations and Ru, examples of which are Li + , Ni 2+ , Ni 3+ , Cu + , Cu 2+ , Mg 2+ , Zn 2+ , B 3+ , Ga 3+ , Al 3+ ,  Mn 3+ , Mn 4+ , Sn 4+ , Sn 4+ , Ti 4+ , and/or Ru 4+/5+/6+ . If M is a mixture of metal cations, the stoichiometric numbers of the metal cations do not have to be equal. If M′ is a mixture of metal cations, the stoichiometric numbers of the metal cations do not have to be equal as long as their sum total (1-y) ranges from 0 to 0.50 (0≤(1-y)&lt;0.50). This new cathode active material can include 1% to 50% Li 2 MO 3  (0.01≤x≤0.50), preferably 1% to 30% (0.01≤x≤0.30). 
     Such active material compositions can be used in rechargeable lithium cells and batteries. Unlike conventional active materials, this new cathode active material uses Li 2 MO 3  to stabilize its structure during repeated lithium intercalation and de-intercalation. The resulting structure contains a Li 2 MO 3  domain, which inherently contains the LiM 6  component that stabilizes the entire cathode active material structure during battery charging and discharging. This makes it possible to reversibly extract more lithium ion from the structure. For example, the disclosed cathode active material composition may provide greater than 60% reversible lithium-ion extraction (reversible capacity of cathode active material &gt;165 mAh/g), and possibly greater than 75% reversible lithium-ion extraction (reversible capacity of cathode active material &gt;200 mAh/g) of the cathode active material&#39;s theoretical capacity. 
     In the disclosed embodiments, the Li 2 MO 3 -stabilized lithium transition metal oxide is preferably synthesized from a mixed-metal hydrated hydroxide precursor previously made by a solution co-precipitation method. This method provides for the best homogeneous mix of transition metals in the intercalation host. In a second method, the material is synthesized using a solid-state reaction. 
     The following examples describe the principles of the disclosed embodiments as contemplated by the inventors, but they are not to be construed as limiting examples. 
     Example 1 
     A layered material with composition represented by 0.02Li 2 MnO 3 ·0.98LiNi 0.021 Co 0.979 O 2 , was made by the solid-state reaction of 9.3623 g of LiOH.H 2 O and 19.6491 g of hydrated Ni 0.02 Mn 0.02 Co 0.96 (OH) 2 .nH 2 O hydroxide pink powder made by a co-precipitation method. This constitutes a material with Ni+3 and Mn+4 as nominal oxidation states. The powders were mixed in an orbital mixer. Following mixing, the mixed powder was transferred to an alumina high-temperature tray and heated first in flowing oxygen gas at 500° C. for 10 hours. The ramp rate of the furnace for this first step was 2° C. per minute. The sample was cooled in the furnace after it was turned off. The sample was subsequently ground by mortar and pestle, then sieved and re-fired at 1050° C. in flowing oxygen gas for 5 hours; the ramp rate was 2° C. per minute, and after firing was completed, a natural cool rate of the furnace turned off was used. The final sintered black powder was broken up and ground by mortar and pestle, then sieved for use in an electrochemical test as a cathode active material, as described in further detail below with respect to Example 4. 
     Scanning electron micrographs (SEMs) of the final powder were taken using a JEOL Nikon Neoscope SEM instrument. An exemplary micrograph is shown in  FIG. 3 . Primary particle sizes range from about 20 to about 100 nm in size; secondary particle sizes range from about 10 to about 16 microns in size. 
     The sample was characterized by X-ray powder diffraction (XRD) at the Argonne National Laboratory synchrotron X-ray research facility, also known as the Advanced Photon Source (APS). The data was converted to Cuk α , radiation. As shown in  FIG. 4 , the XRD pattern of the sample matches the JCPDS hexagonal layered structure of lithium cobalt oxide (LCO). 
     The sample was characterized by Raman spectroscopy on an InVia Renishaw Raman Microprobe.  FIG. 5  shows the Raman vibrational spectrum of the sample 0.02Li 2 MnO 3 .0.98LiNi 0.021 Co 0.979 O 2  synthesized in Example 1. The result shows a shoulder mode at 650 cm −1  and another of lesser intensity at ˜450 cm −1 . For reference the LCO Raman spectrum is also plotted. Note that these shoulders do not appear in the pure hexagonal layered structure of LCO. These shoulder vibrations, therefore, are indicative of low energy transition metal oxygen modes associated with Example 1 material. 
     Example 2 
     A layered material with composition represented by 0.04Li 2 MnO 3 ·0.96LiCoO 2  was made by the solid-state reaction of 4.63 g of LiOH.H 2 O and 9.0 of hydrated Mn 0.04 Co 0.96 (OH) 2 .nH 2 O hydroxide pink powder made by a co-precipitation method. This composition is representative of a Ni-free, Mn+4 nominal oxidation state. The powders were mixed in an orbital mixer. Following mixing, the mixed powder was transferred to an alumina high-temperature tray and heated first in air at 500° C. for 10 hours. The ramp rate of the furnace for this first step was 2° C. per minute. The sample was cooled in the furnace after it was turned off. The sample was subsequently ground by mortar and pestle, then sieved and re-fired at 1050° C. in air for 5 hours; the ramp rate was 2° C. per minute, and after firing was completed, a natural cool rate of the furnace turned off was used. The final sintered black powder was broken up and ground by mortar and pestle, then sieved for use in an electrochemical test as a cathode active material. SEMs of the final powder were taken using a JEOL Nikon Neoscope SEM instrument. An exemplary micrograph is shown in  FIG. 6 . Secondary particle sizes range from about 10 to about 30 microns in size. 
     Example 3 
     The cathode active material synthesized in Example 1 was processed into electrode laminates. Each electrode laminate was created by making a slurry of 90 wt. % cathode active material, 5 wt. % carbon and 5 wt. % polyvinylidene fluoride (PVDF) binder in an NMP (N-methyl-pyrrolidone) solvent. The slurry was cast onto an aluminum current collector sheet using a doctor blade. The wet electrode laminate was first dried at 75° C. for ˜4 hours in an air oven, followed by heated vacuum drying at 75° C. overnight (˜16 hours). The electrode laminate was calendared. Electrodes of size 9/16″ diameter were punched out from the aluminum sheet and built into size 2032 coin cells (Hohsen, Japan). The coin cells contained lithium as counter electrodes (e.g., anodes) and an electrolyte mixture of 3:7 (wt., EC:EMC) solvent and 1.2 M LiPF 6  salt. The separator was Celgard 2325 tri-layer polypropylene. 
     Cells were placed on a Maccor Series 2000 tester and cycled in galvanostatic mode at room temperature with various voltage windows: 4.4V to 2.75V, 4.5V to 2.75V, 4.6V to 2.75V, and 4.7V to 2.75V. A series of electrochemical tests of formation, rate, and cycling were conducted under each voltage window. During formation testing, a constant current (0.2C) was applied to the cell during the charge process, followed by a constant voltage charge until the current was equal to or less than 0.05C. Then, the cells were discharged at constant current (0.2C) until the end of discharge. Charging and discharging of the cells were repeated three times. During rate testing, the charging rate was fixed to 0.7C for all the rate tests, and then followed by constant voltage charge until the current was equal to or less than 0.05C. Five different discharge rates of 0.1C, 0.2C, 0.5C, 1C, and 2C were applied until the cells were completely discharged. Three cycles were conducted for each rate. Finally, 50 cycles were conducted to investigate cycle life. The same charging conditions as those of the rate test were applied. The discharge rate was fixed to 0.5C for all the cycles. 
     The cell&#39;s voltage profile using the first charge-discharge curve between 2.75 and 4.6 V is shown in  FIG. 7 . The capacity versus cycle number for the cell is shown in  FIG. 8 , including the rate and cycle performance study.  FIG. 9  shows XRD patterns of two electrodes containing the cathode active material: a first electrode after 50 cycles and a pristine second electrode. There remains a strong layered peak (003) that resides in the inventive material sample, and no impurity peaks are present. A summary of cycling data and performance metrics for the above-described battery cell is shown in Table 1 below. 
     
       
         
           
               
               
             
               
                   
                 TABLE 1 
               
             
            
               
                   
                   
               
               
                   
                 Charge Voltage (V) 
               
            
           
           
               
               
               
               
               
               
            
               
                   
                 Rate 
                 4.4 
                 4.5 
                 4.6 
                 4.7 
               
               
                   
                   
               
            
           
           
               
               
               
               
               
               
            
               
                 1st Cycle Formation 
                 0.2 C 
                 177.11 
                 194.77 
                 231.99 
                 261.58 
               
               
                 Charge Capacity, mAh/g 
               
               
                 1st Cycle Formation 
                 0.2 C 
                 167.00 
                 183.73 
                 218.19 
                 245.36 
               
               
                 Discharge Capacity, 
               
               
                 mAh/g 
               
               
                 1st Cycle Formation 
                 0.2 C 
                 94.29% 
                 94.33% 
                 94.05% 
                 93.80% 
               
               
                 Efficiency (%) 
               
               
                 1st avg. discharge voltage 
                 0.2 C 
                 3.97 
                 4.01 
                 4.10 
                 4.14 
               
               
                   
               
            
           
         
       
     
     Example 4 
     The cathode active material synthesized in Example 2 was processed into electrode laminates to evaluate its electrochemical performance. Each electrode laminate was formed by making a slurry of 90 wt. % active material, 5 wt. % Super P carbon and 5 wt. % PVDF binder in an NMP solvent. The slurry was cast onto an aluminum current collector sheet using a doctor blade. The wet electrode laminate was dried first at 70-80° C. for ˜4 hours in an air oven, and then followed by heated vacuum drying at 70-80° C. overnight (˜16 hours). The electrode laminate was calendared. Electrodes of size 9/16″ diameter were punched out from the aluminum sheet and built into size 2032 coin cells (Hohsen, Japan). The coin cells contained lithium as counter electrodes (e.g., anodes) and an electrolyte mixture of 3:7 (wt., EC: EMC) solvent and 1.2 M LiPF 6  salt. The separator was Celgard 2325 tri-layer polypropylene. 
     Cells were placed on a Maccor Series 2000 tester and cycled in galvanostatic mode at room temperature with various voltage windows: 4.4V to 2.75V, 4.5V to 2.75V and 4.6V to 2.75V. A series of electrochemical tests (e.g., formation with results shown in  FIGS. 10A-C , rate with results shown in  FIGS. 10D-F ) were conducted under each voltage window. During formation testing, a constant current (0.2C) was applied to the cells during the charge process, followed by a constant voltage charge until the current was equal to or less than 0.05C. Then, the cells were discharged at constant current (0.2C) until the end of discharge. Charging and discharging of the cells were repeated three times. During rate testing, the charging rate was fixed to 0.7C for all the rate tests, and then followed by constant voltage charge till the current was equal to or less than 0.05C. Five different discharge rates of 0.1C, 0.2C, 0.5C, 1C, and 2C were applied until the cells were completely discharged. Three cycles were conducted for each rate. The dQ/dV derivative plot between 2.75V and 4.5V for the material prepared from Example 2 is shown in  FIG. 10G . A lack of peaks at 4.1V to 4.3V indicates that there is no phase change for hexagonal to monoclinic in this inventive material. 
     Example 5 
     A material having the composition 0.01Li2MnO3·0.99LiNi0.01Mn0.01Cu0.98O2 is disclosed. In this example, the Ni and Mn content are not equal, and therefore, as written, the Ni oxidation state is nominally +2, and the Mn oxidation state is nominally +4. 
     A layered material with composition represented by 0.01Li 2 MnO 3 ·0.99LiNi 0.01 Mn 0.01 Co 0.98 O 2  was made by the solid-state reaction of 23.0 g of LiOH.H 2 O and 11.1 of hydrated Ni 0.01 Mn 0.02 Co 0.97 (OH) 2 .nH 2 O hydroxide pink powder made by a co-precipitation method. The powders were mixed in an orbital mixer. Following mixing, the mixed powder was transferred to an alumina high-temperature tray and heated first in air at 500° C. for 10 hours. The ramp rate of the furnace for this first step was 2° C. per minute. The sample was cooled in the furnace after it was turned off. The sample was subsequently ground by mortar and pestle, then sieved and re-fired at 1050° C. in air for 5 hours; the ramp rate was 2° C. per minute, and after firing was completed, a natural cool rate of the furnace turned off was used. The final sintered black powder was broken up and ground by mortar and pestle, then sieved for use in an electrochemical test as a cathode active material. Scanning electron micrographs (SEMs) of the final powder were taken using a JEOL Nikon Neoscope SEM instrument. An exemplary micrograph is shown in  FIG. 11 . Secondary particle sizes range from about 10 to about 30 microns in size. 
     Example 6 
     The cathode active material synthesized in Example 5 was processed into electrode laminates to evaluate its electrochemical performance. Each electrode laminate was formed by making a slurry of 90 wt. % active material, 5 wt. % Super P carbon and 5 wt. % PVDF binder in an NMP solvent. The slurry was cast onto an aluminum current collector sheet using a doctor blade. The wet electrode laminate was dried first at 70-80° C. for ˜4 hours in an air oven, and then followed by heated vacuum drying at 70-80° C. overnight (˜16 hours). The electrode laminate was calendared. Electrodes of size 9/16″ diameter were punched out from the aluminum sheet and built into size 2032 coin cells (Hohsen, Japan). The coin cells contained lithium as counter electrodes (e.g., anodes) and an electrolyte mixture of 3:7 (wt., EC: EMC) solvent and 1.2 M LiPF 6  salt. The separator was Celgard 2325 tri-layer polypropylene. 
     Cells were placed on a Maccor Series 2000 tester and cycled in galvanostatic mode at room temperature with various voltage windows: 4.4V to 2.75V, 4.5V to 2.75V, and 4.6V to 2.75V. A series of electrochemical tests (e.g., formation with results shown in  FIGS. 12A-12C , rate with results shown in  FIGS. 12D-12F ) were conducted under each voltage window. During formation testing, a constant current (0.2C) was applied to the cells during the charge process, followed by a constant voltage charge until the current was equal to or less than 0.05C. Then, the cells were discharged at constant current (0.2C) until the end of discharge. Charging and discharging of the cells were repeated three times. During rate testing, the charging rate was fixed to 0.7C for all the rate tests, and then followed by constant voltage charge till the current was equal to or less than 0.05C. Five different discharge rates of 0.1C, 0.2C, 0.5C, 1C, and 2C were applied until the cells were completely discharged. Three cycles were conducted for each rate. 
     To evaluate the cycle performance of the material, cells were placed on test and operated between 4.5V and 2.75V, as shown in  FIG. 12G . After the rate study test was completed as indicated in  FIG. 12G , then the next 50 cycles were discharged at 0.2C and charge at 0.2C. The galvanostatic charge was followed by constant voltage charge till the current was equal to or less than 0.05C. The dQ/dV derivative plot between 2.75V and 4.5V for the material prepared from Example 5 is shown in  FIG. 12H . A lack of peaks at 4.1V to 4.3 V indicates that there is no phase change for hexagonal to monoclinic in this inventive material. 
     The above-described rechargeable battery cell can generally be used in any type of electronic device. For example,  FIG. 13  illustrates a portable electronic device  1300  which includes a processor  1302 , a memory  1304  and a display  1308 , which are all powered by a battery  1306 . Portable electronic device  1300  may correspond to a laptop computer, mobile phone, PDA, tablet computer, portable media player, digital camera, and/or other type of battery-powered electronic device. Battery  1306  may correspond to a battery pack that includes one or more battery cells. Each battery cell may include an anode containing an anode current collector and an anode active material disposed over the anode current collector. The battery cell may also include a cathode containing a cathode current collector and a cathode active material disposed over the cathode current collector. The cathode and anode may be sealed in a flexible pouch. 
     The cathode active material may have a composition represented by xLi 2 MO 3 ·(1-x)LiCo y M′ (1-y) O 2 . M may be manganese, titanium, ruthenium, and/or zirconium. M′ may be a monovalent cation, a divalent cation, a trivalent cation, a tetravalent cation, and/or a ruthenium cation. For example, M or M′ may contain a mixture of metal cations with stoichiometric numbers that may or may not be equal. In addition, 0.01≤x≤0.50 and 0.5≤y≤1.00. Alternatively, y=1.00, M is Mn, and the composition is xLi 2 MnO 3 ·(1-x)LiCoO 2 . 
     The foregoing descriptions of various embodiments have been presented only for purposes of illustration and description. They are not intended to be exhaustive or to limit the present invention to the forms disclosed. Accordingly, many modifications and variations will be apparent to practitioners skilled in the art. Additionally, the above disclosure is not intended to limit the present invention.

Metadata:
Filing Date: 20140312
Publication Date: 20200407
Grant Date: 20200407
Priority Date: 20130312
Inventors: DAI, HONGLI
JOHNSON, CHRISTOPHER S.
WU, HUIMING
Assignee: APPLE INC
CPC Classifications: [{"code": "H01M4/525", "inventive": true, "first": true, "tree": "[]"}, {"code": "H01M4/505", "inventive": true, "first": false, "tree": "[]"}, {"code": "H01M4/505", "inventive": true, "first": false, "tree": "[]"}, {"code": "H01M10/0525", "inventive": true, "first": false, "tree": "[]"}, {"code": "H01M4/525", "inventive": true, "first": true, "tree": "[]"}, {"code": "H01M4/131", "inventive": true, "first": false, "tree": "[]"}, {"code": "H01M4/131", "inventive": true, "first": false, "tree": "[]"}, {"code": "H01M10/0525", "inventive": true, "first": false, "tree": "[]"}, {"code": "H01M4/525", "inventive": true, "first": true, "tree": "[]"}, {"code": "H01M10/0525", "inventive": true, "first": false, "tree": "[]"}, {"code": "H01M4/131", "inventive": true, "first": false, "tree": "[]"}, {"code": "H01M4/505", "inventive": true, "first": false, "tree": "[]"}, {"code": "Y02P70/50", "inventive": false, "first": false, "tree": "[]"}, {"code": "Y02E60/10", "inventive": false, "first": false, "tree": "[]"}]
Family ID: 51528459