ANODE MATERIAL FOR RECHARGEABLE LI-ION BATTERIES
20230317937 · 2023-10-05
Inventors
Cpc classification
H01M4/485
ELECTRICITY
C01P2002/76
CHEMISTRY; METALLURGY
H01M4/525
ELECTRICITY
C01P2002/74
CHEMISTRY; METALLURGY
C01P2002/77
CHEMISTRY; METALLURGY
H01M4/505
ELECTRICITY
Y02E60/10
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
C01G31/006
CHEMISTRY; METALLURGY
C01P2002/72
CHEMISTRY; METALLURGY
H01M10/0525
ELECTRICITY
International classification
H01M4/485
ELECTRICITY
H01M4/36
ELECTRICITY
H01M4/505
ELECTRICITY
H01M4/525
ELECTRICITY
H01M4/62
ELECTRICITY
Abstract
Materials, designs, methods of manufacture, and devices are provided for an anode material for a rechargeable lithium-ion battery. For example, an anode material may include Li.sub.3±xV.sub.2±yO.sub.5±z, wherein 0≤x≤7, 0≤y≤1, and z may be based on the charge resulting from Li.sub.3±x and V.sub.2±y. Also, a cell can include a lithiated anode material. The lithiated anode material may include Li.sub.3±xV.sub.2±y O.sub.5±z. The lithiated anode material may be casted on a first substrate to form a lithiated anode, having a separator stacked on the lithiated anode. The separator may include electrolytes. A cathode can be stacked on the separator. The cathode being formed by casting a cathode material on a second substrate.
Claims
1. An anode material comprising Li.sub.3±xV.sub.2±yO.sub.5±z, wherein 0≤x≤7, 0≤y≤1, and z is based on the charge resulting from Li.sub.3±x and V.sub.2±y.
2. The anode material of claim 1, wherein the Li.sub.3±xV.sub.2±yO.sub.5±z is an omega structure, wherein the omega structure is a disordered rocksalt structure in the Fm
3. The anode material of claim 1, wherein lithium is reversibly inserted to form at least one of Li.sub.4V.sub.2±yO.sub.5±z and Li.sub.5V.sub.2±yO.sub.5±Z.
4. The anode material of claim 3, wherein the Li.sub.4V.sub.2±yO.sub.5±Z or Li.sub.5V.sub.2±yO.sub.5±Z is an omega structure, wherein the omega structure is a disordered rocksalt structure in the Fm
5. The anode material of claim 1, wherein the composition further comprises a dopant M, such that the composition is defined by Li.sub.3V.sub.xM.sub.yO.sub.5±z, wherein 0.5<x<2, 0<y<1, and z is based on a charge from Li.sub.3, V.sub.x, and M.sub.y.
6. The anode material of claim 5, wherein the Li.sub.3V.sub.xM.sub.yO.sub.5±z is an omega structure, wherein the omega structure is a disordered rocksalt structure in the Fm
7. The anode material of claim 5, further comprising reversibly inserting lithium to form Li.sub.4V.sub.xM.sub.yO.sub.5±z or Li.sub.5V.sub.xM.sub.yO.sub.5±z.
8. The anode material of claim 7, wherein the Li.sub.4V.sub.xM.sub.yO.sub.5±z or the Li.sub.5V.sub.xM.sub.yO.sub.5±z is an omega structure, wherein the omega structure is a disordered rocksalt structure in the Fm
9. The anode material of claim 5, wherein the dopant is selected from the group comprising one or more of Mg, Ca, Sc, B, Y, Al, Ti, Zr, Nb, Ta, Cr, Mo, or W.
10. The anode material of claim 1, further comprising one or more materials selected from the group of silicon, tin, graphite, or non-graphitized carbon, wherein the one or more materials are blended with the anode material to fabricate the anode.
11. The anode material of claim 1, wherein the anode material is added into the electrode, wherein the electrode comprises one or more materials selected from the group of silicon, tin, graphite, or non-graphitized carbon, and wherein the one or more materials are blended with the anode material to fabricate the anode.
12. The anode material of claim 1, wherein the anode material is paired with a cathode, and wherein the cathode is selected from the group comprising one or more of LiFePO.sub.4, LiMn.sub.2O.sub.4, LiNi.sub.0.5Mn.sub.1.5O.sub.4, LiNi.sub.aCo.sub.bMn.sub.cO.sub.2 where a+b+c=1, or other cathodes.
13. The anode material of claim 1, wherein the anode material is a disordered rocksalt structure in the Fm
14. The anode material of claim 13, wherein a lithiated anode material is formed by applying a reducing agent to a powder, wherein the lithiated anode material comprises an omega structure Li.sub.3±xV.sub.2±yO.sub.5±z, wherein 0≤x≤7, 0≤y≤1, and z is based on the charge resulting from Li.sub.3±x and V.sub.2±y wherein the omega structure is a disordered rocksalt structure in the Fm
15. The anode material of claim 10, wherein the anode material comprises an omega structure, wherein the omega structure is a disordered rocksalt structure in the Fm
16. The anode material of claim 5, further comprising one or more materials selected from the group of silicon, tin, graphite, or non-graphitized carbon, wherein the one or more materials are blended with the anode material to fabricate the anode.
17. A method of manufacturing a cell, the method comprising: casting an anode material on a first substrate to form an anode, wherein the anode material comprises V.sub.2O.sub.5, LiV.sub.2O.sub.5, or Li.sub.2V.sub.2O.sub.5; pressing lithium on the anode to form a pressed anode; casting a cathode material on a second substrate to form a cathode; stacking a separator on the pressed anode; stacking the cathode on the separator; injecting the separator with electrolytes, thereby synthesizing the pressed anode into a lithiated anode; and surrounding the anode, the separator, and the cathode with a packet foil to form a cell.
18. The method of claim 17, wherein the anode material further comprises one or more materials selected from the group of silicon, tin, graphite, or non-graphitized carbon that are blended with the V.sub.2O.sub.5, the LiV.sub.2O.sub.5, or the Li.sub.2V.sub.2O.sub.5.
19. A method of manufacturing a cell, the method comprising: casting an anode material on a first substrate to form an anode, wherein the anode material comprises V.sub.2O.sub.5, LiV.sub.2O.sub.5, or Li.sub.2V.sub.2O.sub.5; forming a lithiated anode by applying a reducing agent to an anode, wherein the reducing agent comprises lithium, wherein the lithiated anode comprises an omega structure Li.sub.3V.sub.2O.sub.5, wherein the omega structure is a disordered rocksalt structure in the Fm
20. The method of claim 19, wherein the anode material further comprises one or more materials selected from the group of silicon, tin, graphite, or non-graphitized carbon that are blended with the V.sub.2O.sub.5, the LiV.sub.2O.sub.5, or the Li.sub.2V.sub.2O.sub.5.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0035] Various embodiments are disclosed herein and described in detail with reference to the following figures. The drawings are provided for purposes of illustration only and merely depict typical or example embodiments of the disclosed technology. These drawings are provided to facilitate the reader's understanding of the disclosed technology and shall not be considered limiting of the breadth, scope, or applicability thereof. It should be noted that for clarity and ease of illustration these drawings are not necessarily made to scale.
[0036]
[0037]
[0038]
[0039]
[0040]
[0041]
[0042]
[0043]
[0044]
[0045]
[0046]
[0047]
[0048]
[0049]
[0050]
[0051]
[0052]
[0053]
[0054]
[0055]
[0056]
[0057]
[0058]
[0059]
[0060]
[0061]
[0062]
[0063]
[0064]
[0065]
[0066]
[0067] The figures are not intended to be exhaustive or to limit the invention to the precise form disclosed. It should be understood that the invention can be practiced with modification and alteration, and that the disclosed technology be limited only by the claims and the equivalents thereof.
DETAILED DESCRIPTION
[0068] In the past decades, rechargeable Li-ion batteries have made mobile devices and personal computers an essential necessity in a modern day society. While important advancements in battery technology (e.g., energy density and structural stability) have continued, fast charging is an area that still requires significant advances for Li-ion batteries. Li-ion batteries may possess high energy density; however, the rate at which the battery can charge may be affected by the corresponding anode material of the battery.
[0069] Currently, graphite is used as an anode and operates at a potential similar to lithium metal plating (about 90 mV). Under rapid charging, the lithium metal plates onto the graphite surfaces, which leads to capacity fading, potential internal shorting, and safety incidents. Lithium titanium oxide (Li.sub.4Ti.sub.5O.sub.12) may also be used as an anode. Lithium titanium oxide may be capable of rapid charging. However, lithium ion batteries using lithium titanium oxide have a cell voltage of about 1.4 V less than that of graphite-based cells. The cell voltage may be reduced from about 3.7 V to about 2.3 V. Thus, an anode material with a high rate capability that operates between about 0.1 V and about 1V is disclosed.
[0070] Disclosed are materials, designs, methods of manufacture, and devices related to fast-charging Li-ion batteries. The fast-charging Li-ion battery may include substrates, an anode material, a cathode, an electrolyte, a separator, and a packet foil. The Li-ion batteries may be able to charge on the scale of minutes instead of hours. The battery may be one or more of a pouch-type, cylinder, button, prismatic, or other battery types. In embodiments, the cell may be formed to have the specifications as listed in Table 1. All of the values listed in this disclosure are approximate, unless expressly indicated otherwise.
TABLE-US-00001 TABLE 1 Cell design for 2 Ah pouch cell. Dimension Thickness, max (mm) 4.5 Cathode Capacity (mAh/g) 190 Active Material Loading 90% Coating Weight (mg/cm.sup.2 each side) 14.3 Areal Capacity (mAh/cm.sup.2 each side) 2.45 Electrode Press Density (g/cm.sup.3) 2.86 Electrode Length (mm) 56 Electrode Width (mm) 43 Electrode Thickness (single side) (um) 45 Al Foil Thickness (um) 15 Double Layers 17 Anode Cell Balance (N/P ratio) 1.08 Capacity (mAh/g) 300 Active Material Loading 90% Coating Weight (mg/cm.sup.2 each side) 9.8 Areal Capacity (mAh/cm.sup.2 each side) 2.64 Electrode Press Density (g/cm.sup.3) 2.26 Electrode Length (mm) 58 Electrode Width (mm) 45 Electrode Thickness (single side) (um) 39 Cu Foil Thickness (um) 10 Double Layers 18 Electrolyte Electrolyte/Capacity (g/Ah) 3 Weight (g) 6 Separator Total Wrapping Length (mm) 1750 Thickness (um) 20 Packet Foil Thickness (um) 115 Cell Voltage (V) 3.2 Capacity (mAh) 2031 Energy (mWh) 6499 Weight (g) ~32 Energy density (Wh/kg) >200
[0071] For example, a battery may be used for powering personal electronics to cars, neighborhoods, and other systems. A battery may include a group of cells. Cells may be individual electrochemical units including individual assemblies. In some embodiments, the cell voltage may range from about 1 volt to about 5 volts. In embodiments, the capacity may range from about 1500 mAh to about 50000 mAh. In some embodiments, the cell may have an energy ranging from about 1500 mWh to about 250000 mWh. In some embodiments, the cell may have an energy density ranging from about 150 Wh/kg to about 500 Wh/kg.
[0072] The cell may include a cathode. The cathode may include one or more of LiMn.sub.2O.sub.4, LiNi.sub.xCo.sub.yMn.sub.zO.sub.2 where x+y+z=1, and other cathodes. The cathode may be paired with a given anode based on corresponding compositions.
[0073] In embodiments, the cathode may have a capacity ranging from about 50 mAh/g to about 300 mAh/g. In some embodiments, the active material loading may range from about 50% to about 100%. In embodiments, the coating weight for each side may range from about 3 mg/cm.sup.2 to about 25 mg/cm.sup.2. In some embodiments, the areal capacity may represent the energy capacity as a function of the size of a given battery. The areal capacity for each side of the cathode may range from about 0.5 mAh/cm.sup.2 to about 10 mAh/cm.sup.2.
[0074] In some embodiments, the cathode press density may range from about 0.5 g/cm.sup.3 to about 10 g/cm.sup.3. Aluminum foil may be used as a substrate upon which to place the cathode material. In embodiments, the cathode material may be cast, laminated, pressed, or otherwise coupled to the aluminum foil. In some embodiments, the aluminum foil thickness may range from about 1 um to about 50 um. It should be appreciated that other materials may be used as a substrate for the cathode. The number of double layers may range from about 5 to about 50.
[0075] As described above, the cell may include anode material. The anode material may be able to facilitate a Li-ion battery charging on the scale of minutes without a complicated nanosizing process. The anode material could enable a fast charge battery without sacrificing energy density. In embodiments, the anode material may show a voltage plateau ranging from about 0 V to about 1 V. In some embodiments, the voltage plateau may be about 0.5 V. The range of the voltage potential may ensure that under high current, the electrode potential achieves a value that does not cause lithium plating. The range of the voltage potential may also ensure that the cell voltage does not decrease to less than about 3.0 V, when a common cathode material is used. The anode material may work at a voltage at about 0.5V, which reduces the risk of lithium plating but results in a lithium-ion battery with cell voltage about 1 V higher than that with a Li.sub.4Ti.sub.5O.sub.12 anode, as discussed above.
[0076] In embodiments, the anode material includes V.sub.2O.sub.5. In some embodiments, the V.sub.2O.sub.5 electrode may be lithiated. Lithiating may include treating a material or substance with lithium or one of its compounds. In some embodiments, the lithiated V.sub.2O.sub.5 may form one or more of Li.sub.3V.sub.2O.sub.5, Li.sub.5V.sub.2O.sub.5, and other compositions with the general formula Li.sub.xV.sub.2O.sub.5, where 3≤x≤5. The Li.sub.3V.sub.2O.sub.5 may be introduced as an anode material that enables two lithium to be reversibly inserted to form Li.sub.5V.sub.2O.sub.5. In some embodiments, inserting lithium into the V.sub.2O.sub.5 can form an omega structure Li.sub.3V.sub.2O.sub.5, which may be a disordered rocksalt structure in the Fm
[0077] In some embodiments, Li.sub.3V.sub.2O.sub.5 may represent a base composition to which dopants may be added. The composition may have a rocksalt structure, into which two more lithium can be inserted into Li.sub.3V.sub.2O.sub.5 to form a nominal composition of Li.sub.5V.sub.2O.sub.5, where the rocksalt structure is still preserved in the Li.sub.5V.sub.2O.sub.5 composition. The general formula for the composition may be Li.sub.3±xV.sub.2±yM.sub.yO.sub.5±z, wherein 0≤x≤7, 0≤y≤2, and where z depends on the combined positive charge of Li, V and M so that the oxygen balances out the combined positive charge. M may be a dopant used in addition to, or instead of, V. In some embodiments, the dopants may include one or more metal dopants. The metal dopants may include one or more divalent, trivalent, tetravalent, pentavalent, or hexavalent dopants, such as Mg, Ca, Sc, B, Y, Al, Ti, Zr, Nb, Ta, Cr, Mo, W, or other metal dopants.
[0078] The omega structure may be a disordered rocksalt structure in the Fm
[0079] In embodiments, the anode may include active materials, conductive carbon additives, binders, and additional Li sources. In some embodiments, active material may include one or more of the above disclosed anode materials and other active materials. In embodiments, conductive additives may improve the life cycle of a cell as well as the energy density of a cell. Conductive carbon additives may include one or more of carbon nanotubes, carbon blacks, ultra-fine carbon, and other carbon additives. In some embodiments, binders may hold active material together as well as place them in contact with the foil corresponding to an electrode. The binders may also help keep conductive carbon additives in place against the active material. The binders may include one or more of homopolymers, copolymers, polyvinylidene fluoride, styrene butadiene copolymer, and other binders.
[0080] In some embodiments, the anode may have a negative to positive electrode (N to P) ratio, ranging from about 0.8 to about 1.5. In embodiments, the anode may have a capacity ranging from about 100 mAh/g to about 500 mAh/g. In some embodiments, the active material loading may range from about 50% to about 100%. In embodiments, the coating weight for each side may range from about 3 mg/cm.sup.2 to about 25 mg/cm.sup.2. In some embodiments, the areal capacity for each side of the anode may range from about 0.5 mAh/cm.sup.2 to about 10 mAh/cm.sup.2.
[0081] In some embodiments, the electrode press density may range from about 0.5 g/cm.sup.3 to about 10 g/cm.sup.3. Copper foil may be used as a substrate upon which to place the anode material. In embodiments, the anode material may be cast, laminated, pressed, or otherwise coupled to the copper foil. In some embodiments, the copper foil thickness may range from about 1 um to about 200 um. It should be appreciated that other materials may be used as a substrate for the anode. In embodiments, the number of double layers may range from about 5 to about 50.
[0082] Electrolytes may be used to fill the separator that promotes the movement of ions between the cathode and the anode during charge and discharge (e.g., during charge the ions move from cathode to anode; while discharging the ions move from anode to cathode). In some embodiments, the electrolyte may have an electrolyte/capacity value ranging from about 1 g/Ah to about 10 g/Ah. In some embodiments, the electrolytes may include organic solvents selected from one or more of ethylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and other organic solvents. The electrolytes may further include lithium salts, such as LiPF.sub.6, LiCIO.sub.4, LiBF.sub.4, LiAsF.sub.6, LiTFSI, LiFSI, and other salts. TFSI may refer to bis(trifluoromethanesulfonyl)imide and FSI refers to Bis(fluorosulfonyl)imide.
[0083] The separator may insulate the cathode from the anode. The separator may have no electrical conductivity. The separator may be made of one or more of rubber, glass fiber, cellulose, polyethylene plastic, polyolefin, and other materials. The separator may be porous to hold the electrolyte. In some embodiments, the pore size ranges from about 10 nm to about 150 nm. The separator may be made to close the pores when the temperature breaches a threshold to prevent the reaction from escalating. In some embodiments, the separator may be coated with another material that will close over the pores to prevent overheating.
[0084] The packet foil may insulate the anode-separator-cathode assembly from an external environment. The packet foil may range from about 50 um to about 200 um.
[0085] It should be appreciated that while individual values within the ranges need not be achieved, the ratios between one or more values may be relevant in scaling the cell for different applications. The ranges are provided as example embodiments of cells for a given application, and it should be appreciated that different ranges may be appropriate for different applications.
[0086]
[0087]
[0088]
[0089] In the first 100 or so cycles, the anode material was subjected to a current density of about 100 mA/g where the greatest loss in capacity is shown. In the remaining cycles, a current density of about 200 mA/g is used and the capacity is shown as staying substantially around 90 mAh/g.
[0090]
[0091]
[0092]
[0093]
[0094]
[0095]
[0096] Crystal structure model 1510 may be the omega structure of Li.sub.3V.sub.2O.sub.5. The omega structure may be similar to a disordered rocksalt structure with a Fm
[0097] Oxygen ions 1511 may be close-packed in crystal structure model 1510, serving as a frame for the rocksalt structure of Li.sub.3V.sub.2O.sub.5. In crystal structure model 1510, the oxygen ions 1511 may be located at the corners and face centers. Lithium ions and vanadium ions may be located at the edge centers, represented by the other spheres. The lithium and vanadium ions 1514 may sit in the octahedral sites coordinated by, as illustrated, six oxygen ions. Part of the lithium ions 1512 may occupy the tetrahedral sites coordinated by, as illustrated, four oxygen ions.
[0098]
[0099]
[0100]
[0101]
[0102]
[0103]
[0104]
[0105]
[0106]
[0107]
[0108]
[0109]
[0110]
[0111]
[0112]
[0113]
[0114] While various embodiments of the disclosed technology have been described above, it should be understood that they have been presented by way of example only, and not of limitation. Likewise, the various diagrams may depict an example architectural or other configuration for the disclosed technology, which is done to aid in understanding the features and functionality that can be included in the disclosed technology. The disclosed technology is not restricted to the illustrated example architectures or configurations, but the desired features can be implemented using a variety of alternative architectures and configurations. It will be apparent to one of skill in the art how alternative functional, logical or physical partitioning and configurations can be implemented to implement the desired features of the technology disclosed herein. Additionally, with regard to flow diagrams, operational descriptions and method claims, the order in which the steps are presented herein shall not mandate that various embodiments be implemented to perform the recited functionality in the same order unless the context dictates otherwise.
[0115] Although the disclosed technology is described above in terms of various exemplary embodiments and implementations, it should be understood that the various features, aspects and functionality described in one or more of the individual embodiments are not limited in their applicability to the particular embodiment with which they are described, but instead can be applied, alone or in various combinations, to one or more of the other embodiments of the disclosed technology, whether or not such embodiments are described and whether or not such features are presented as being a part of a described embodiment. Thus, the breadth and scope of the technology disclosed herein should not be limited by any of the above-described exemplary embodiments.
[0116] Terms and phrases used in this document, and variations thereof, unless otherwise expressly stated, should be construed as open ended as opposed to limiting. As examples of the foregoing: the term “including” should be read as meaning “including, without limitation” or the like; the term “example” is used to provide exemplary instances of the item in discussion, not an exhaustive or limiting list thereof; the terms “a” or “an” should be read as meaning “at least one,” “one or more” or the like; and adjectives such as “conventional,” “traditional,” “normal,” “standard,” “known” and terms of similar meaning should not be construed as limiting the item described to a given time period or to an item available as of a given time, but instead should be read to encompass conventional, traditional, normal, or standard technologies that may be available or known now or at any time in the future. Likewise, where this document refers to technologies that would be apparent or known to one of ordinary skill in the art, such technologies encompass those apparent or known to the skilled artisan now or at any time in the future.
[0117] The presence of broadening words and phrases such as “one or more,” “at least,” “but not limited to” or other like phrases in some instances shall not be read to mean that the narrower case is intended or required in instances where such broadening phrases may be absent.
[0118] Additionally, the various embodiments set forth herein are described in terms of exemplary block diagrams, flow charts and other illustrations. As will become apparent to one of ordinary skill in the art after reading this document, the illustrated embodiments and their various alternatives can be implemented without confinement to the illustrated examples. For example, block diagrams and their accompanying description should not be construed as mandating a particular architecture or configuration.