KR20210141785A - Rechargeable battery cells and packs with high capacity, expandable temperature range, and high tolerance for overcharging and discharging misuse - Google Patents

Abstract

Provided is an electrochemical secondary battery that exhibits excellent misuse tolerance in overdischarge and overcharge conditions including at extreme temperatures, remains robust, and has excellent performance. The battery provided herein has the formula Li _1+x MO _2+y (where -0.9≤x≤0.3, -0.3≤y≤0.3, and M contains 80 atomic% or more of Ni based on the total M ), wherein the cathode electrochemically active material comprises a non-uniform distribution of Co and the cathode and formula Li _4+a Ti ₅ O _12+b , wherein -0.3 ≤a≤3.3, -0.3≤b≤0.3) an anode comprising an anode comprising an electrochemically active material, wherein the anode and the cathode each independently comprise a current collector substrate comprising aluminum.

Description

Rechargeable battery cells and packs with high capacity, expandable temperature range, and high tolerance for overcharging and discharging misuse

Government Support Statement

This invention is awarded by the U.S. Army contract W56HZV-12-C-0065, the U.S. Navy contract N39430-14-C-1506, the U.S. Department of Energy contract DE-SC0013739, and the U.S. Department of Defense Procurement Service. This was done with government support under one contract, HQ0147-15-C-8003. The government has certain rights in this invention.

technical field

The present invention relates to lithium ion secondary batteries and uses thereof.

BACKGROUND Lithium-ion batteries are the primary power source for many portable electronic devices for a variety of reasons, including the high energy density, high specific energy, and long cycle life associated with the technology. However, commercially available lithium ion batteries pose safety concerns, especially when mechanically abused. Lithium-ion batteries cannot be charged rapidly or at very low temperatures, and generally perform poorly at low temperatures. Lithium-ion batteries can suffer from severe safety failures, especially when subjected to mechanical abuse that causes internal short circuits. Lithium-ion batteries are sensitive to over-discharge and over-charge, and when the battery or battery cell is over-charged or over-discharged, it can exhibit undesirable loss of performance and unsafe events. In addition, long-term storage or transportation of commercially available lithium-ion batteries can be problematic due to their susceptibility to over-discharge.

To avoid these and other safety concerns, the cells of currently available lithium-ion batteries are electronically monitored and their state of charge controlled, which can be done using a battery management circuit (BMC). In addition to preventing overdischarging of lithium ion cells and preventing degradation mechanisms such as copper dissolution, the battery management circuitry can also provide overcharge protection. The cell monitoring and state of charge control used in current lithium-ion batteries is often more than that used in other rechargeable battery technologies such as lead acid or nickel metal hydride batteries, and in many applications, battery management circuitry is required. may be omitted.

Without wishing to be bound by theory, it is understood that the overdischarge susceptibility of current lithium ion batteries arises from the combination of the graphite anode material and the copper current collector material used. Copper is used because it is not susceptible to electrochemical alloying with lithium at the electrochemical potential of graphite. However, copper can be oxidized when the anode is driven to a high potential, which can occur if the cell is overdischarged. It is understood that the oxidized copper will redeposit in a fibrous form, which can limit its lifespan, and subsequent recharging of the cell can potentially cause an internal short circuit.

For high-capacity rechargeable battery applications, especially where low temperature performance and ability to recharge very quickly are desirable, or where the battery must be able to safely survive extreme abuse, better than lithium-ion cells using graphite or other low-potential anode materials. The use of techniques that provide lower energy densities and/or lower specific energies may be acceptable. For example, lead-acid batteries, despite the fact that they provide the energy density fraction and specific energy provided by lithium-ion batteries, are currently used in vehicle ignition and start-stop battery applications, such as "start-light-ignition" (SLI) applications. However, when the duty cycle of a vehicle ignition or start-stop battery application is extended and the battery is cycled over a larger range of states of charge, since the duty cycle of the application extends beyond the classic SLI type of duty cycle, The performance and lifespan of lead-acid batteries can be inadequate.

Accordingly, there is a need for battery technologies that provide the desirable characteristics of lithium-ion batteries, such as long cycle life, and some of the characteristics currently provided by lead acid SLI batteries, such as high capacity, fast recharge and low temperature performance. There is also a great need for techniques that provide improved safety, including, for example, the ability to safely withstand extreme mechanical abuse and operate safely down to 0V, without external circuitry to protect against overdischarge.

The following is provided to facilitate the understanding of some of the unique innovative characteristic features of the present invention, and is not intended to be an exhaustive description. A thorough understanding of the various aspects of the invention can be obtained by taking the entire specification, claims, drawings and abstract as a whole.

Rechargeable lithium ion battery that is robust, very safe, exhibits high power transfer and capacity, has a long cycle life, has good performance at high and low temperatures, is very resistant to mechanical abuse, and can be stored for an extended period of time and packs are disclosed.

Surprisingly, it has been found that the electrochemical cells of the present invention are resistant to extreme mechanical abuse and continue to function as electrochemical cells, ie, support charging and discharging even after such mechanical abuse. The cells of some aspects provided herein may be discharged and charged at cryogenic temperatures, stored at zero volts for extended periods of time without damage, are resistant to overcharging without damage to the cell, or a combination thereof.

The battery provided herein has the formula Li _1+x MO _2+y (where -0.9≤x≤0.3, -0.3≤y≤0.3, and M contains Ni in 80 atomic% or more based on the total M ) defined by or comprising a polycrystalline cathode comprising a cathode formed of an electrochemically active material. In addition, cathode electrochemically active materials are characterized by a non-uniform distribution of Co on, within or throughout the particles. The cell further comprises an anode comprising an anode electrochemically active material _{of the formula Li 4+a} Ti ₅ O _{12+b, wherein -0.3≤a≤3.3, -0.3≤b≤0.3, the anode} And each of the cathodes independently includes a current collector substrate formed of or including aluminum.

The cell may be of any configuration, such as a cylindrical or pouch cell.

The anode and cathode are in ion contact with a separator and are separated by the separator. The separator may include or be a polymeric separator. In some aspects, the separator may include a polyolefin. In some aspects, the separator may further comprise a ceramic coated on one or more of the separator surfaces, or optionally embedded in a polymer on one or more of the separator surfaces. The ceramic may be a ceramic such as a ceramic oxide. In some aspects, the separator is or comprises aluminum oxide.

The cells of the present invention have the ability to be configured in an anode limited fashion. Thus, the area ratio of the anode to the cathode is arbitrarily less than or equal to one. Additionally or alternatively, the capacity ratio of the anode electrochemically active material to the cathode electrochemically active material is 1 or less.

Solvents and electrolytes that may include salts may be included. Optionally the solvent is a carbonate solvent or a combination of one or more carbonate solvents with other suitable substances. _{The salt is optionally a lithium salt, optionally a LiPF 6} salt in a mixture of propylene carbonate, ethyl methyl carbonate and methyl butyrate.

The anode and cathode may comprise a binder mixed with the anode active material, the cathode active material. The binder is any polymeric binder optionally comprising or consisting of PVdF.

An electrochemical cell according to the present invention may be described more fully below with reference to the accompanying drawings in which various aspects are shown. However, this invention may be embodied in many different forms and should not be construed as limited to the aspects set forth herein. Rather, these aspects are provided so that this will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art. Like reference numbers refer to like elements throughout. BRIEF DESCRIPTION OF THE DRAWINGS These and other aspects, advantages and characteristic features of the present invention will become more apparent by further detailed description of exemplary embodiments thereof with reference to the accompanying drawings, in which:
1 is a schematic diagram of an aspect of a lithium ion cell with details of a stack of electrodes on the right.
2 shows voltage (volts, V) versus capacity (ampere-hours, Ah) for various rates of charging and discharging at room temperature of a cell in accordance with some aspects provided herein.
3 shows voltage (volts, V) versus capacity (ampere-hours, Ah) for various rates of charging and discharging at -50° C. for a cell in accordance with some aspects provided herein.
4 shows cell discharge capacity (mAh) versus cycle number for fast cycling at 45° C. of two cells in accordance with some aspects provided herein.
5 shows voltage (volts, V) versus capacity (mAh) for each of charge (A) and discharge (B) at various constant powers at room temperature, in accordance with some aspects provided herein.
6 depicts cell voltage (volts, V) versus voltage reversal at room temperature and electrode V (volts, V) versus time elapsed in minutes versus Li reference, in accordance with some aspects provided herein.
7 shows voltage (volts) versus capacity (Ah) for discharge at room temperature before and after reversal of a cell in accordance with some aspects provided herein.
8 shows voltage (volts) versus capacity discharged (mAh) for repeated fast pulsed discharges at -18° C. before and after reversal of a cell according to some aspects provided herein.
9 depicts cell voltage (volts, V) for a 10% overcharge at room temperature and electrode V (volts, V) versus time elapsed in minutes versus Li reference, in accordance with some aspects provided herein; .
10 shows voltage (volts) versus capacity (Ah) versus discharge at room temperature before and after overcharge of a cell in accordance with some aspects provided herein.
11 shows voltage (volts) versus discharge capacity (mAh) for repeated fast pulsed discharges at -18°C before and after overcharging of a cell in accordance with some aspects provided herein.
12 shows voltage (volts, V) versus capacity (ampere-hours) for various rates of charge and discharge at room temperature before and after undergoing extensive cycling and subsequent storage at 0V conditions, in accordance with some aspects provided herein; , Ah) is shown.
13 depicts voltage (volts, V) and temperature (° C.) versus time elapsed in seconds during a nail penetration abuse test, in accordance with some aspects provided herein.
14 illustrates voltage (volts, V) versus capacity (ampere-hours, Ah) for discharge at room temperature before and after being subjected to round bar crush testing, in accordance with some aspects provided herein; show
15 is a photograph showing the integrity and continued function of a cell in accordance with some aspects provided herein after undergoing a number of extreme mechanical abuses.
16 shows voltage (volts, V) versus capacity (ampere-hours, Ah) versus discharge at room temperature before and after being subjected to multiple extreme mechanical abuses of a cell in accordance with some aspects provided herein.
17 depicts cell discharge capacity (Ah) versus number of cycles for continuous cycling after undergoing multiple extreme mechanical abuses of a cell according to some aspects provided herein.

Surprisingly, a positive electrode comprising a polycrystalline cathode electrochemically active material having a non-uniform distribution of cobalt, and a negative electrochemically active material comprising lithium titanate (LTO) optionally having an electrochemical redox potential of about 1.55 volts relative to lithium A lithium ion battery of the present invention has been found comprising an anode comprising Unexpectedly, the cells of the present invention continue to function electrochemically without significant loss of performance after such abuse. In addition, the battery of the present invention has an intrinsic ability to accommodate very high charge rates, has excellent recovery after long-term storage in deep discharge conditions (eg 0V), It can be charged at high speed (eg 1C) at the same very cold temperature. Accordingly, the cells of the present invention solve many of the problems associated with other battery systems and technologies by providing an exceptionally robust and safe battery system that can be used in many cell types, including pouch cells, and for many different applications. .

As used herein, “absorption” may refer to an intercalation or intercalation or conversion alloying reaction of lithium with an active material. Absorption may be referred to herein as “lithiation”.

As used herein, “desorption” may refer to interlayer desorption or desorption or conversion dealloying reaction of lithium and an active material. Desorption may be referred to herein as "delithiation".

As used herein in reference to a lithium ion battery, "cathode" means a positive electrode and "anode" means a negative electrode.

As used herein, an “active material” is a material that participates in the electrochemical charge/discharge reaction of an electrochemical cell, for example by absorbing or desorbing lithium.

The lithium ion battery disclosed herein can be safely discharged to 0V without affecting its performance. In addition, such a lithium ion battery can safely withstand high levels of overcharge and voltage reversal, and the ability to withstand voltage reversal allows the batteries to be connected in series without handling individual cells and discharged to 0V. Because the lithium ion cells and batteries disclosed herein can be discharged to 0V, many benefits are provided. For example, the lithium ion cells and batteries disclosed herein may be stored and/or shipped in a discharged state to provide improved safety. Due to the high resistance to overcharging and overdischarging of the cell, a battery made from the cell can withstand loss or failure of battery management while maintaining performance and lifespan at safe and useful levels. In addition, the lithium ion cells provided herein can be charged very quickly at low temperatures without affecting their safety, performance or lifespan, making them well suited for applications such as electric load leveling and start-stop vehicle batteries. . In addition, this lithium ion battery has excellent stability at high temperatures and good performance at very low temperatures.

Without wishing to be bound by any one particular theory, it is believed that the choice of anode structure and material is highly helpful in providing several unique properties of the electrochemical cells provided herein. One strategy for providing lithium ion batteries that can be discharged to zero volts or stored in a discharged state while at least preventing decomposition of commonly used copper current collectors is to , titanium or stainless steel is used for the current collector. However, titanium and stainless steel are less conductive than copper. For example, the conductivity of copper is more than 20 times that of titanium. As a result, the rate performance of a cell using titanium or stainless steel instead of copper may be lower than that using copper. Therefore, for some applications, the rate performance provided by cells using titanium or stainless steel current collectors is not sufficient. The use of a titanium or stainless steel current collector may provide improved overdischarge performance, but the use of titanium or stainless steel may render the cell unsuitable for applications where high capacity performance is required.

As provided herein, the problems associated with other metals commonly used for the current collector is, with lithium at a potential less than 0.1 volts to 0.5 volts for the electric potential, Li / Li ⁺ of less than 0.5 volts to Li / Li ⁺ It is solved by providing an electrochemical cell comprising a current collector for a negative electrode comprising an electrochemically reactive metal, for example aluminum, or made of the metal alone. The provided aluminum current collector can be used with a negative electrochemically active material comprising LTO because the electrochemical potential of LTO is higher than that in an aluminum alloy with lithium. For example, LTO according to some aspects provided herein has an electrochemical oxidation-reduction potential of 1.55 volts against Li / Li ^+, for this oxidation-reduction potential is the potential of Li / Li ⁺ of the aluminum alloy with lithium greater than 0.4V. Therefore, when LTO having an electrochemical redox potential of 1.55 volts with respect to lithium is used, problems related to copper such as copper dissolution can be prevented by using aluminum for the current collector of the negative electrode. Also, without wishing to be bound by theory, it is believed that the solid electrolyte interphase (SEI), which is understood to contain electrolyte reduction products, does not form on the LTO due to its higher potential compared to lithium. . This property, combined with the ability to safely discharge to 0V, creates a lithium-ion battery with unexpectedly improved safety and stability.

In addition, since a negative electrode containing LTO, which has an electrochemical redox potential of 1.55 volts with respect to lithium, is easily electrochemically kinetic, and Li intercalation is very reversible, and a current collector containing aluminum is relatively conductive, such a negative electrode Lithium ion batteries comprising can provide high rate capability for both charging and discharging and excellent lifetime.

As such, the electrochemical cell provided herein includes a negative electrode comprising LTO as an anode electrochemically active material, the LTO being coated on an aluminum current collector. In some aspects, the positive electrode comprises a polycrystalline cathode electrochemically active material coated on an aluminum current collector. The aluminum current collector is optionally in the form of a sheet formed of Al or an aluminum alloy, and may be in the form of a foil, a solid substrate, a porous substrate, a grid, a foam or a foam coated with aluminum, or other forms known in the art. In some aspects, the aluminum current collector is a foil. Optionally, the grid may include an expanded metal grid and a perforated foil grid.

The positive electrode also includes a current collector. The current collector for the positive electrode may be formed of aluminum, for example, an aluminum alloy. The aluminum current collector is optionally in the form of a sheet and may be in the form of a foil, a solid substrate, a porous substrate, a grid, a foam or a foam coated with aluminum or other forms known in the art. In some aspects, the aluminum current collector is a foil. Optionally, the grid may include an expanded metal grid and a perforated foil grid.

A current collector for the anode or cathode is optionally associated with a tab that can be used to electrically connect the cell to a circuit for use. Each of the anode current collector and the cathode current collector may be electrically connected to the tab. The tab may be made of any suitable material, such as aluminum or other materials known in the art. The tab is optionally an uncoated area of the current collector. For stacked cells with multiple anodes and cathodes, the tabs can be welded together to form a single positive tab and a single negative tab for connection to external circuitry.

The cathode of the electrochemical cell provided herein serves as the anode. The cathode comprises a polycrystalline cathode electrochemically active material capable of adsorbing and desorbing Li. The cathode electrochemically active material provided herein is a material of the formula Li _1+x MO _2+y , wherein -0.9≤x≤0.3, -0.3≤y≤0.3, and M is based on the total M It contains 80 atomic% or more of Ni. A polycrystalline material includes agglomeration or association of a plurality of crystallites to form a polycrystalline material. Within the polycrystalline material, each crystallite may have any suitable shape, which may be the same or different within each secondary particle of the cathode electrochemically active material. Also, the shape of each crystallite may be the same or different in different particles. The microcrystals may be faceted due to their crystalline properties, the microcrystals may have a plurality of flat surfaces, and the shape of the microcrystals may approximate a geometric shape. The microcrystals may optionally be polyhedral. The microcrystals may have a straight shape, and some or all of the microcrystals may be straight when viewed in cross section. The microcrystals may be square, hexagonal, rectangular, triangular, or combinations thereof.

The cathode electrochemically active material contains Ni as a major component of the M component. The amount of Ni in the first composition is optionally 80 to 100 atomic % (at %) of the total M. Optionally, the Ni component of M is at least 80 at%. Optionally, the Ni component of M is at least 85 at%. Optionally, the Ni component of M is at least 90 at%. Optionally, the Ni component of M is at least 95 at%. Optionally, the Ni component of M is at least 75at%, at least 76at%, at least 77at%, at least 78at%, at least 79at%, at least 80at%, at least 81at%, at least 82at%, at least 83at%, at least 84at%, at least 85at% , 86at% or more, 87at% or more, 88at% or more, 89at% or more, 90at% or more, 91at% or more, 92at% or more, 93at% or more, 94at% or more, 95at% or more, 96at% or more, 97at% or more, 98at % or more, 99at% or more, 99.5at% or more, 99.9at% or more, or 100at% or more.

In some aspects, M is Ni alone or in combination with one or more additional elements. The further element is optionally a metal. Optionally, the additional element may include or be one or more of Al, Mg, Co, Mn, Ca, Sr, Zn, Ti, Y, Cr, Mo, Fe, V, Si, Ga or B. . In certain aspects, the additional element may include Mg, Co, Al, or combinations thereof. Optionally, the additional element may be Mg, Al, V, Ti, B or Mn or combinations thereof. Optionally, the further element is selected from the group consisting of Mg, Al, V, Ti, B or Mn. Optionally, the further element is selected from the group consisting of Mg, Co and Al. Optionally, the further element is selected from the group consisting of Ca, Co and Al. In some aspects, the additional element is Mn or Mg or both Mn and Mg. Optionally, the additional element is Mn, Co, Al, or any combination thereof. Optionally, the additional elements include Co and Mn. Optionally, further elements are Co and Al. Optionally, the further element is Co.

The additional element of M in the cathode electrochemically active material may be present in an amount from about 0.1 to about 20 at%, specifically from about 5 to about 20 at%, more specifically from about 10 to about 20 at% of M in the first composition. have. Optionally, the additional element may be present in an amount from about 1 to about 20 at%, specifically from about 2 to about 18 at%, more specifically from about 4 to about 16 at% of M in the first composition. In some illustrative examples, M is about 80-100 at% Ni, 0-15 at% Co, 0-15 at% Mn, and 0-10 at% additional elements.

The cathode electrochemically active material used in the cathode of the cell provided herein comprises Co, wherein the Co is non-uniformly distributed through, on, or in the secondary particles of the cathode electrochemically active material. . A non-uniform distribution is a distribution of Co that varies over some or all of the secondary particles. In some aspects, the polycrystalline material includes grain boundaries between adjacent crystallites within secondary particles, wherein the concentration of cobalt, aluminum, or both is higher at the grain boundaries than at the centers of the adjacent crystallites. These materials are considered to be grain boundary-rich materials. Illustrative examples of such grain boundary-rich materials can be found in US Pat. No. 9,391,317 and US Pat. No. 16/250,762.

In certain aspects, the secondary particles used as the cathode electrochemically active material have grain boundaries rich in Co, Al, or both, optionally the mole fraction of Co, Al or both at the grain boundaries is optionally the sum of the respective regions. higher than the mole fraction of Co, Al, or both in the crystallites as an average over

The composition of microcrystals, grain boundary regions, or both optionally has a layered α-NaFeO ₂ type structure, a cubic structure, or a combination thereof. The aspect in which the grain boundary has a layered α-NaFeO ₂ type structure can be specifically mentioned. Another aspect with grain boundaries with a defective α-NaFeO _{2 type structure is specifically mentioned.} Another aspect in which some of the grain boundaries have a cubic or spinel structure is specifically mentioned.

The grain boundaries are optionally _{formed with a second composition of formula I Li 1+x} MO _2+y (formula 1), wherein -0.9≤x≤0.3, -0.3≤y≤0.3, and M is Co, Al or a combination of Co and Al. Optionally in the second composition M further comprises Ni. Optionally, the Ni component of M in the second composition is 1 at% or less. Optionally, the Ni component of M is 5 at% or less. Optionally, the Ni component of M is 10 at% or less. Optionally, the Ni component of M is 20 at% or less. Optionally, the Ni component of M is 75 at% or less. Optionally, the Ni component of M is 80 at% or less. Optionally, the Ni component of M is 90at% or less. Optionally, the Ni component of M is 95 at% or less. Optionally, the Ni component of M is 98 at% or less. Optionally, the Ni component of M is 99 at% or less.

In a grain boundary rich cathode electrochemically active material, the concentration of Co, Al or both averaged over the grain boundary region is higher than the average concentration of Co, Al or both averaged over the grain boundary region. As such, the mole fraction of Co, Al or both at the grain boundary is higher than the mole fraction of Co, Al or both in the microcrystals. The mole fraction of Co, Al or both in the first composition, as determined by ICP, as defined when Co, Al or both are not present at all in the crystallites, is that the composition of the crystallites is equal to the total particle lower than the single or combined mole fraction of total Co or Al in the composition. The single or combined mole fractions of Co and Al in the microcrystals may be zero. The single or combined mole fraction of Co and Al in the second composition defined at the grain boundary is higher than the single or combined mole fraction of Co and Al in the whole grain, as measured by ICP. The second composition may be enriched with 0 to 8 at%, optionally 3 to 5 at% Co, optionally supplemented with 0.01 to 10 at% Al, optionally up to 1.5 at% Al.

Optionally, the second composition and the first composition (microcrystalline composition) are identical except for the presence or concentration (mol fraction) of Co, Al or both increased in the second composition relative to the first composition.

The cathode electrochemically active material optionally comprises a non-uniform distribution of Co in the secondary particles, wherein the non-uniform distribution is in the form of a gradient of Co within the crystallites, within the overall secondary particles, or combinations thereof. Optionally, the microcrystals include a Co concentration gradient in which the amount of Co at or near the periphery of the microcrystals is greater than the concentration of Co at or near the center of the microcrystals. Illustrative examples of such materials are described in Lim, et al., Adv. Funct. Mater. 2015; 25:4673-4680 or in Lee et al., Journal of Power Sources , 2015; 273:663-669].

In some aspects, the non-uniform distribution of Co is described in U.S. Patent No. 7,381,496, U.S. Patent Application Publication No. 2016/0181611, or Zuo, et al., Journal of Alloys and Compounds , 2017; 706:24-40] by coating the core with Co.

The positive electrode may be provided by combining lithium nickel oxide, a conductive agent and a binder, and providing a coating comprising the lithium nickel oxide, a conductive agent and a binder on the current collector. The conductive agent may be any conductive agent that provides suitable properties, and may be amorphous, crystalline, or a combination thereof. The conductive agent may include carbon black, such as acetylene black or lamp black, mesocarbon, graphite, carbon fibers, carbon nanotubes, such as single-walled carbon nanotubes or multi-walled carbon nanotubes, or combinations thereof. can

The binder used in the anode or cathode may be any binder that provides suitable properties, including polyvinylidene fluoride, copolymers of polyvinylidene fluoride, polyvinylidene difluoride (PVdF), hexafluoropropylene, poly(vinyl acetate), poly(vinyl butyral-co-vinyl alcohol-co vinyl acetate), poly(methylmethacrylate-co-ethyl acrylate), polyacrylonitrile, polyvinyl chloride-co-vinyl acetate, Polyvinyl alcohol, poly(l-vinylpyrrolidone-co-vinyl acetate), cellulose acetate, polyvinylpyrrolidone, polyacrylate, polymethacrylate, polyolefin, polyurethane, polyvinyl ether, acrylonitrile- butadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene-styrene, triblock polymers of sulfonated styrene/ethylene-butylene/styrene, polyethylene oxide, or combinations thereof.

The positive electrode contains lithium nickel oxide, a conductive agent and a binder in an appropriate ratio, for example, 80 to 98 wt % lithium nickel oxide, 2 to 20 wt % conductivity, based on the total weight of the lithium nickel oxide, conductive agent and binder. agent and 2 to 10 wt % of a binder. The lithium nickel oxide, conductive agent and binder may be suspended in a suitable solvent, for example N-methylpyrrolidinone or other suitable solvent, disposed on a suitable substrate such as aluminum foil, and dried in air to form the positive electrode. can provide

The electrochemical cells provided herein further include a negative electrode. The negative electrode comprises lithium titanium oxide (LTO) optionally having an electrochemical redox potential of about 1.5 V with respect to lithium. The lithium titanium oxide may have a spinel-type structure.

The anode may optionally _{comprise an anode electrochemically active material of the formula Li 4+a} Ti ₅ O _12+b (2), wherein -0.3≤a≤3.3 and -0.3≤b≤0.3. In some aspects, the lithium titanium oxide can be of Formula 3:

Li _4+y Ti ₅ O ₁₂ (3)

In Formula 3, 0≤y≤3, 0.1≤y≤2.8, or 0≤y≤2.6.

Alternatively, the lithium titanium oxide may be of formula (4).

Li _3+z Ti _6-z O ₁₂ (4)

In the formula (4), 0≤z≤1. optionally 0≤z≤1, 0.1≤z≤0.8, or 0≤z≤0.5. Combinations of anode electrochemically active materials comprising at least one of the lithium titanium oxides may be used. In some aspects, the anode electrochemically active material is including Li ₄ Ti ₅ O ₁₂ having an electrochemical oxidation-reduction potential of about 1.55V for lithium or Li ₄ Ti ₅ O _12.

The lithium titanium oxide may have any suitable particle size, for example, from about 0.1 to about 100 μm or from about 1 to about 10 μm.

The lithium titanium oxide may have a high specific surface area (SSA), for example, from about 4 to about 20 m ² /g or from about 7 to about 13 m ² /g.

The negative electrode includes a current collector. As discussed further above, without wishing to be bound by theory, it is believed that since the ^{electrochemical potential of lithium titanium oxide with respect to Li/Li +} is greater than 1 volt, the negative electrode current collector may include a metal other than copper. This is understood because other metals such as aluminum and titanium provide adequate stability at the potentials present when lithium titanium oxide with an electrochemical redox potential of greater than 1 volt relative ^{to Li/Li + is used.} Without wishing to be bound by theory, when using graphite as the anode material, copper is not, because metals such as aluminum are electrochemically reactive with lithium at potentials of 0.1 to 0.5 volts relative to lithium, whereas copper is not. It is understood to be used as a current collector material. Therefore, a current collector comprising a metal that electrochemically reacts with lithium at a potential of 0.1 to 0.5 V, 0.15 to 0.45 V or 0.2 to 0.4 V with respect to lithium cannot be used as a graphite anode material, but can be used for an LTO anode material. can

The current collector of the anode, cathode or both may comprise aluminum, reference is made to aluminum or an aluminum alloy. Representative aluminum alloys include aluminum alloys 1050, 1100, 1145, 1235, 1350, 3003, 3105, 5052 and 6061.

The negative electrode may be formed by combining the anode LTO, the conductive agent and the binder, and providing a coating comprising the LTO, the conductive agent and the binder on the current collector selected for the negative electrode. The conductive agent may be any conductive agent that provides suitable properties, and may be amorphous, crystalline, or a combination thereof. The conductive agent may be carbon black, such as acetylene black or lamp black, mesocarbon, graphite, carbon fibers, carbon nanotubes, such as single-walled carbon nanotubes or multi-walled carbon nanotubes, or combinations thereof. . The binder may be any binder that provides suitable properties, including polyvinylidene fluoride, PVdF, copolymers of polyvinylidene fluoride and hexafluoropropylene, poly(vinyl acetate), poly(vinyl butyral-co- vinyl alcohol-co vinyl acetate), poly(methylmethacrylate-co-ethyl acrylate), polyacrylonitrile, polyvinyl chloride-co-vinyl acetate, polyvinyl alcohol, poly(l-vinylpyrrolidone-co) -vinyl acetate), cellulose acetate, polyvinylpyrrolidone, polyacrylate, polymethacrylate, polyolefin, polyurethane, polyvinyl ether, acrylonitrile-butadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene- styrene, a triblock polymer of sulfonated styrene/ethylene-butylene/styrene, polyethylene oxide, or combinations thereof, and the like.

The negative electrode comprises LTO, a conductive agent and a binder in an appropriate ratio, for example, 80 to 98 wt % LTO, 2 to 20 wt % conductive agent and 2 to 10 wt % LTO, based on the total weight of the LTO, conductive agent and binder. It can be prepared by combining the binders of The LTO, conductive agent and binder may be suspended in a suitable solvent such as N-methylpyrrolidinone, placed on a suitable current collector such as aluminum, titanium or stainless steel, and dried in air to provide the negative electrode. .

The positive and negative electrodes can be fabricated with loadings (mass of coated material per unit area of current collector) tailored to the desired speed performance and voltage range for a particular application. Higher power (higher speed) applications require lower loading electrodes to maximize electrode interface surface area and minimize current density, while applications requiring higher energy densities can be combined with current collectors and separators. A higher loading electrode is required to minimize the cell content of the same inert material.

A further advantage of an LTO anode, optionally having an electrochemical redox potential of about 1.55 volts relative to lithium, is that its potential is positive enough to prevent lithium metal plating potential under all but the most extreme overcharge conditions, the anode It can be implemented in a limiting cell design. This anode-limited cell design can improve the overcharge tolerance and stability of the cell by limiting the delithiation of the charged cathode to a level commensurate with the voltage per cell required for a particular application. As such, the electrochemical cells provided herein are optionally limited in area, loading, or otherwise.

Optionally, the electrochemical cell is anode limited because the geometric surface area of the cathode is optionally greater than or equal to the geometric surface area of the anode. Therefore, the area ratio obtained by dividing the area of the cathode by the area of the anode is 1 or less. Optionally, the area ratio of anode to cathode is 0.99 or less, 0.98 or less, 0.97 or less, 0.96 or less, 0.95 or less, 0.94 or less, 0.93 or less, 0.92 or less, 0.91 or less, 0.90 or less, 0.85 or less, 0.80 or less, 0.75 or less, 0.70 or less. , 0.65 or less, 0.60 or less, 0.55 or less, or 0.50 or less. In some aspects, the geometric areas of the anode and cathode are the same or substantially the same.

Optionally, the capacity ratio of the anode to the cathode is 1 or less. The electrode capacity ratio is the ratio of the cathode capacity to the anode capacity. The capacity of an electrode is often given as the product of charging time per unit area. The units of charge and time used are not critical in the ratio calculation. The capacitance of the electrode is equal to the capacitance per unit area multiplied by the electrode area. Accordingly, in the case of two electrodes having a similar area, the capacitance ratio is equal to the ratio of the capacitance per unit area of the two electrodes. Optionally, the capacity ratio of anode to cathode is 0.99 or less, 0.98 or less, 0.97 or less, 0.96 or less, 0.95 or less, 0.94 or less, 0.93 or less, 0.92 or less, 0.91 or less, 0.90 or less, 0.85 or less, 0.80 or less, 0.75 or less, 0.70 or less. , 0.65 or less, 0.60 or less, 0.55 or less, or 0.50 or less.

In some aspects of a provided electrochemical cell, the unit cell includes an anode, a cathode, and a separator positioned between the anode and the cathode, wherein an electrolyte is provided in ionic contact with the anode and cathode. Optionally, the unit cell is one comprising a double-sided anode in which the anode electrochemically active material is coated on both sides of a current collector, or the cathode is a double-sided cathode in which both sides of the current collector are coated by a cathode electrochemically active material. The two-side electrode may be flanked on both sides by two single-sided opposite electrodes or another opposite double-sided electrode. In this way, a stack of electrodes may be provided to form a unit cell. In some aspects, two single side anode electrodes comprising LTO coated on an aluminum current collector, a polyolefin separator, and a double side cathode electrode coated on both sides of an aluminum current collector are provided. These unit cells are stacked to form an electrochemical cell. In some aspects, a single side anode electrode is located at the end of such a stack, although it is understood that the end electrode of the stack may be a cathode.

The positive electrode, the negative electrode and the separator may be combined in a housing to provide a lithium ion battery, one aspect of which is shown in FIG. 1 . The lithium ion battery 100 includes a positive electrode 101 having a positive electrode tab 101 ′; a negative electrode 102 having a negative electrode tab 102'; and a separator 103 interposed between the anode 101 and the cathode 102 . The cell may include an electrolyte in ion contact with both an anode and a cathode. Ionic contact means that the electrolyte can transfer ions from the anode to the cathode or from the cathode to the anode.

An electrochemical cell includes a separator positioned between an anode and a cathode in the unit cell. The separator may be formed of a microporous membrane, optionally a porous film comprising a polyolefin such as polypropylene, polyethylene, or combinations thereof. In some aspects, the separator may further comprise a coating of a ceramic oxide material, optionally aluminum oxide, or a fine particulate reinforcing filler. A high output capacity can be provided to the battery by selecting a high permeability separator having a Gurley air permeability of less than 200 seconds per 100 cc.

The anode, cathode, separator, and electrolyte may be housed in a battery case (eg, a housing). The battery case 110 may be a metal can, or may be a laminate film, for example, a heat-sealable aluminum foil, for example, an aluminum-coated polypropylene film. As such, the electrochemical cells provided herein may be of any known cell type, such as a button cell, a pouch cell, a cylindrical cell or other suitable configuration. In some aspects, the housing is in the form of a flexible film, optionally a polypropylene film. Such housings are commonly used to form pouch cells. Lithium ion cells may have any suitable configuration or shape, and may be cylindrical or prismatic.

The cells provided herein are capable of controlling any circuit, such as a battery management circuit, or the rate of charging or the extent of charging or discharging, and optionally excludes other means used in the art.

A lithium ion battery includes an electrolyte in contact with a positive electrode 101 , a negative electrode 102 , and a separator 103 . The electrolyte may include an organic solvent and a lithium salt. The organic solvent may be a mixture of cyclic carbonates and linear carbonates and esters. Representative organic solvents include ethylene carbonate, propylene carbonate, ethyl methyl carbonate, diethyl carbonate, dimethyl carbonate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, methyl butyrate, or combinations thereof. mixtures of propylene carbonate, ethyl methyl carbonate and methyl butyrate.

Representative lithium salts used in the electrolyte are LiPF ₆ , LiBF ₄ , LiAsF ₆ , LiClO ₄ , LiCF ₃ SO ₃ , Li(CF ₃ SO ₂ ) ₂ N, LiN(SO ₂ C ₂ F ₅ ) ₂ , LiSbF ₆ , LiC (CF ₃ SO ₂ ) ₃ , LiC ₄ F ₉ SO ₃ and LiAlCl ₄ , but are not limited thereto. The lithium salt can be dissolved in an organic solvent. Combinations comprising at least one of the above salts and a solvent may be used. The concentration of the lithium salt may be 0.1 to 2 moles (M) in the electrolyte. A 1M LiPF ₆ solution is mentioned.

Electrolytes can be formulated to provide large capacity and low temperature performance. Such electrolytes may have an ionic conductivity greater than 8 mS/cm at 25° C. and greater than 1 mS/cm at −40° C.

Batteries made with lithium ion cells may include any suitable number of cells, such as 1 to 50,000 cells, 2 to 25,000 cells, 4 to 15,000 cells, 8 to 5,000 cells, 16 to 2,000 cells, or 32 to It may contain 1,000 cells. The cells may be connected in any suitable configuration, including a series connection, a parallel connection, or a combination thereof.

The charging and discharging of cells and batteries made therefrom can include any suitable charging and discharging method, and charging and discharging at any suitable rate, for example 100C or lower, 10C or lower, 0.01 to 10C, or 0.1 to 1C. can be The C rate is the discharge rate of the cell, which is the total capacity of the cell divided by the total discharge time time, for example, the C rate of a battery having a discharge capacity of 1.6 amp-hours is 1.6 A. Discharging the battery to 1.4V or less, optionally 1.3V or less, optionally 1.2V or less, optionally 1.1V or less, optionally 1.0V or less, optionally 0.9V or less, optionally 0.8V or less, optionally 0.7V or less, optionally 0.6V or less, optionally 0.5 V or less, optionally 0.4 V or less, optionally 0.3 V or less, optionally 0.2 V or less, optionally 0.1 V or less, such as 0.1 to 0.001 V, 0.05 to 0.005 V. The discharge is optionally a discharge below 0V.

Various aspects of the invention are illustrated by the following non-limiting examples. The examples are for illustrative purposes only and are not limiting on any implementation of the present invention. It will be understood that variations and modifications may be made without departing from the spirit and scope of the invention.

Example

Example 1.

At an active material loading of 11.3 mg/cm ² , LNO-type lithium nickel oxide (CAMX Power, LLC, Lexington, MA) rich in cobalt grain boundaries with a nominal composition of _{Li 1.01} Mg _0.025 Ni _0.88 Co _0.12 Al _0.0064 O _{2 , acetylene black and} A positive electrode was prepared by coating a mixture of polyvinylidene difluoride (PVdF) in a weight ratio of 94:3:3 on aluminum. At an active material loading of 12.7 mg/cm ² _{, a mixture of lithium titanium oxide with a nominal composition Li 4} Ti ₅ O ₁₂ and a specific surface area of 10 m ² /g, acetylene black and PVdF in a weight ratio of 90:3:7 was mixed onto aluminum phase. was coated to prepare a negative electrode. For both the positive and negative electrodes ^{, acetylene black with a surface area of 100 m 2} /g (Denka AB-100 from Denka Carbons) and PVdF with a molecular weight of 1,000,000 to 1,200,000 mol/g (Solef 5130 from Solvay Chemicals) were used.

The anode and cathode had the same geometric area ^{of 72.7 cm 2 .} Twelve double side anode layers and 11 double side cathode layers and two single side cathode layers were stacked into a Z-folded separator assembly. The separator was a 21 μm thick alumina-coated polyolefin material with a Gurley air permeability of 110 seconds. The stack assembly of electrodes was placed in an aluminum coated polypropylene envelope with electrode tabs supplied through the edge seal of the package, and 1M LiPF in a mixture of propylene carbonate, ethyl methyl carbonate and methyl butyrate in a 1:1:2 weight ratio. _An electrolyte consisting of 6 and having an ionic conductivity of 11 mS/cm at 25° C. and 2 mS/cm at −40° C. was added prior to sealing to give a 3 amp-hour (Ah) laminate packaged prismatic cell weighing 82 g.

The cell was cycled at various rates between 2.75V and 1.4V at room temperature. It was also cycled at -50°C at various rates between 3.0V and 1.2V.

2 is cell voltage (volts, V) versus capacity (ampere-hours) illustrating the voltage profiles of a first charge and discharge of a cell at a rate of 0.6 A, and subsequent charges and discharges at rates of 3 A and 9 A, conducted at room temperature; , Ah) is a graph. A first charge voltage profile of 0.6A exhibits an upturn at about 2.55V, which is characteristic of the anode limiting charge capacity of the design. The cell has high rate performance, as evidenced by a gentle increase in voltage polarization as the current increases from 0.6A (C/5) to 9A (3C).

3 is a graph of cell voltage (volts, V) versus capacity (ampere-hours, Ah) showing voltage profiles for cells charged and discharged at various rates at -50°C, in a range accessible with conventional lithium-ion battery technology; got out of The voltage limit is extended compared to the limit for cycling at room temperature (FIG. 4) to accommodate the higher voltage polarization at the cryogenic temperature. The cell delivers more than half of its capacity when discharged to 0.6A and more than 40% of its capacity when discharged to 10C. Surprisingly, the cell can be charged to almost half its capacity at a rate of 3A (1C) within the 3V charging voltage limit.

Example 2.

Two 120 mAh laminate packaged prismatic cells were prepared using the materials and methods of Example 1, but with the following differences.

The positive active material loading was 9.0 mg/cm ² , and the negative active material loading was 9.4 mg/cm ² . The individual cathode and anode pieces both had an area of 10.2 cm ² and were assembled into a stack with 5 double side anode layers, 4 double side cathode layers + 2 single side cathode layers. The cell was first cycled between 2.43V and 1.33V at room temperature, corresponding to a 6-series cell battery cycled between 14.6V and 8.0V. It was then cycled 1,000 times between 2.43V and 1.33V in an oven at 45°C with a charge rate of 1.2A (10C) and a discharge rate of 1.2A (10C). The cell was free-standing without any external fixturing to maintain the stack pressure in the case of gas during the cycling. After the cycling was complete, the cells were inspected and measured and showed no evidence of any gas release.

FIG. 4 is a graph of 10C discharge capacity versus number of cycles for both cells during cycling at 45° C., showing that the capacity delivered by the cells only decreases by about 5% during this aggressive cycling regime; It is demonstrated that the battery has excellent temperature-rise stability and is not damaged by repeated rapid charging.

Example 3

A 325 mAh laminate packaged prismatic cell designed for very high power capacity was prepared using the materials and methods of Example 1 but with the following differences:

The positive electrode active material loading was 3.6mg / cm ^2, the anode active material loading was 3.7mg / cm ^2. The individual cathode and anode pieces had an area of 10.2 cm ² and were assembled into a stack with 36 double side anode layers, and 35 double side cathode layers plus 2 single side cathode layers. The separator was a 6 μm thick polyolefin material with a Gurley air permeability of 100 seconds. The weight of the finished battery was 13.5 g, and the volume was 7.2 cc.

The cell was cycled between 2.59V and 1.31V at room temperature, which corresponds to an 11-series cell battery cycled between 28.5V and 14.4V at various constant power levels. 5 shows two graphs, respectively, of voltage (volts, V) versus capacity (mAh) versus charging and discharging of the battery at various power levels, respectively, indicating the significantly higher power capacity of the battery. At a constant specific power of more than 5 kW/kg and a constant power of 80 W, which corresponds to a power density of more than 11 kW/l, the cell maintains a continuous charge for nearly 30 seconds and a continuous discharge for about 11 seconds, resulting in an increase in the capacity of the cell. It provides about 45% and 18.5 Wh/kg constitutes about 35% of the total energy content of the cell.

Example 4

A 3-electrode 130 mAh laminate-packaged prismatic cell was prepared using the materials and methods of Example 1 but with a Li metal reference electrode with the following differences:

The positive active material loading was 9.1 mg/cm ² , and the negative active material loading was 10.0 mg/cm ² . The individual cathode and anode pieces had an area of 10.2 cm ² and were assembled into a stack with 5 double side anode layers, and 4 double side cathode layers plus 2 single side cathode layers.

The performance of the cell was characterized by continuous constant current and pulse charge/discharge cycling between 2.59 V and 1.31 V at room temperature and -18 °C, and the anode (negative) potential was calculated by the difference between the cathode potential and the cell voltage. , the potential of the cathode was monitored by measuring the anode versus Li metal reference electrode voltage when the cell was cycled. The cell was then discharged to 0V and held at that voltage for 24 hours, then overdischarged by an additional 5% (6.5mAh) of the cell's capacity at a rate of 0.1C (i.e., 13mA discharge for 30 minutes) to reverse the voltage. carried out. After reversal, the cell was recharged to re-characterize its performance.

6 is a graph of electrode potential (V versus Li reference) and cell voltage versus time (in minutes) for overdischarge of the cell at a time of 30 minutes and subsequent relaxation of 30 minutes in open circuit. The graph shows that the cell voltage was reversed and reached about -3.5V, and the cathode and anode potential reached about 1.9V for Li and 5.4V for Li, respectively. In an open circuit, the cell voltage increases rapidly, mainly due to a sharp decrease in the high anode potential, while the low cathode potential rises much more slowly, indicating that the voltage polarization at the anode during overdischarge is greater than the voltage polarization at the cathode. shows that the charge passed through the cathode during overdischarge is related to a reversible Faraday process.

7 is a graph of voltage (volts) versus capacity (Ah) for various rates of discharge at room temperature before and after inversion of the cell, showing that the effect of 5% capacity reversal on room temperature discharge characteristics is minimal.

8 is a graph of voltage (volts) versus capacity (mAh) for a continuous 10C (1.3A), 30 second lasting pulse discharge at -18°C before and after the cell was reversed. Cells were rested in open circuit for 30 minutes after each pulse (before the next) to ensure that they did not appreciably self-heat during testing. The cell was able to support the aggressive cold pulsing over 50% of the state of charge range (65 mAh) both before and after reversal, showing that the effect of 5% capacity reversal on cold pulsed power performance was minimal.

Example 5

The materials and methods of Example 4 were used to fabricate a 3-electrode 130 mAh laminate-packaged prismatic cell containing a Li metal reference electrode. The performance of the cell was characterized by continuous constant current and pulsed charge/discharge cycling between 2.59 V and 1.31 V at room temperature and -18 °C, and the anode (negative) potential was calculated by the difference between the cathode potential and the cell voltage. , the potential of the cathode was monitored by measuring the anode versus Li metal reference electrode voltage when the cell was cycled. The cell was then charged to 2.59V and then overcharged by an additional 10% (13mAh) of the cell's capacity at a rate of 0.1C (ie, 13mA charge for 60 minutes). After overcharging, the battery was discharged to characterize its performance again.

9 is a graph of electrode potential (V versus Li reference) and cell voltage versus time in minutes for a cell overcharge of a duration of 60 minutes and subsequent relaxation of 30 minutes in open circuit. The graph shows that the overcharged cell voltage reached about 3.5V and the cathode and anode potential reached about 4.1V for Li and 0.6V for Li, respectively. In the open circuit, the cell voltage decreased due to the increase of the anode potential while the cathode potential did not change, showing that the voltage polarization at the anode during overcharging is greater than at the cathode, with about 20% excess of the cathode. This indicates that the charge passed through the cathode during overcharging is associated with a normal reversible Faraday process, as would be expected in the anode-limited cell design with

10 is a graph of voltage (volts) versus capacity (Ah) for various rates of discharge at room temperature before and after the cell is reversed, showing that the effect of 10% overcharge on room temperature discharge characteristics is minimal. The voltage polarization during 25C discharge was larger than before after overcharge, indicating that overcharge slightly increased the impedance of the cell.

11 is a graph of voltage (volts) versus capacity (mAh) for a continuous 10C (1.3A), 30 second sustained pulse discharge at -18°C before and after the cell was overcharged. Cells were rested in open circuit for 30 minutes after each pulse (before the next) to ensure that they did not appreciably self-heat during testing. The cell was able to support the low temperature pulsing over a discharge range of a depth of 65 mAh before being overcharged and over a discharge range of a depth of 50 mAh after reversing, and the voltage polarization during pulsing was higher than after overcharging. The results of these aggressive low-temperature pulse tests show that the impedance of the cell increased due to overcharging, but nevertheless maintained a high level of performance.

Example 6

A 2.5 Ah laminate packaged prismatic cell was prepared using the materials and methods of Example 1 but with the following differences.

The positive active material loading ^{was 11.2 mg/cm 2} , and the negative active material loading was 12.6 mg/cm ² . The area of the individual cathode and anode pieces was 72.7 cm ² , and they were assembled into a stack with 10 double side anode layers, 9 double side cathode layers + 2 single side cathode layers.

The cell was first charged to 2.75V at 0.5A and then cycled between 2.75V and 1.4V at various rates to evaluate performance. The cell was then cycled 1,000 times between 2.65V and 1.4V at room temperature at a charge rate of 2.5A (1C) and a discharge rate of 2.5A (1C). During the cycling, the cell maintained a continuous capacity of 2.2 Ah. After 1,000 cycles, the cell was discharged to 0V and stored at room temperature for 33 months. After this storage, the cell open circuit voltage was measured to 0V, after which the cell was charged and cycled according to the same protocol used for characterization when freshly built.

12 is a graph of voltage (volts) versus capacity (Ah) for various rate discharges at room temperature before and after the battery has been cycled 1,000 times and then stored for 33 months at 0V condition, wherein the performance of the battery is cycled and extended at 0V; It shows that it did not change significantly by storage. These results demonstrate excellent cycling stability and shelf life at 0V conditions for the battery technology of the present invention. The figure also shows that the first charge to 0.5A after extended 0V storage essentially overlaps the first charge at 0.5A of a freshly made cell, which indicates that the discharge to 0V was at the time the cell was made ( as-made) indicates a return to the condition.

Example 7

A 2.7 Ah laminate-packaged prismatic cell was prepared using the materials and methods of Example 1 but with the following differences.

The positive active material loading was 8.4 mg/cm ² , and the negative active material loading was 9.1 mg/cm ² . The individual cathode and anode pieces had an area of 72.7 cm ² and were assembled into a stack with 15 double side anode layers, and 14 double side cathode layers plus 2 single side cathode layers.

The cell was first charged to 2.65V, then a blunt 2mm diameter stainless steel nail was pushed into the cell at a rate of 1 cm/sec and held in the cell for 1 minute to test the nail penetration in a custom designed device while simultaneously testing the voltage and surface of the cell. The temperature was recorded. 13 is a graph of cell voltage (V) and surface temperature (°C) before, during, and after a nail penetration test. The figure shows that the voltage of the cell decreases very slowly while the nail is in the cell, similar to the voltage change under slow discharge (eg <C/10), which causes a soft short. indicates that This voltage change stopped when the nail was removed, indicating that the short was removed. Similarly, the surface temperature of the cells increased only slightly during nail penetration. These results demonstrate the remarkable resistance of the cell technology to the occurrence of large-capacity dissipation internal short circuits while undergoing penetrating mechanical abuse.

Example 8

A 4Ah laminate packaged prismatic cell was prepared using the materials and methods of Example 1 but with the following differences.

The positive electrode active material loading was 9.3 mg/cm ² , and the negative electrode material loading was 9.0 mg/cm ² .

The individual cathode and anode pieces had an area of 124.9 cm ² and were assembled into a stack with 12 double side anode layers, and 11 double side cathode layers plus 2 single side cathode layers.

The performance of the battery was characterized by first cycling between 2.59V and 1.31V at various rates at room temperature and then charging to 2.75V. The charged cell was then crushed under a 1/2" diameter stainless steel bar placed across a width of 10 cm over a period of 5 minutes in a custom designed device while the voltage and surface temperature of the cell were recorded. During the crushing event, the force applied to the bar was increased to 35 kN (3.8 ton), and the displacement measured by the crusher showed that the thickness of the cell at the maximum crush line was reduced from 5 mm to 0.5 mm. As in the slow discharge, it gradually dropped from 2.556V to 2.552V and the surface temperature increased by 1° C. When the pressure on the bar and the cell was released, the voltage drop stopped and the temperature stopped increasing. After that, the performance of the cell was reduced to 2.59V and Characterization was again confirmed by cycling between 1.31V.

14 is a graph of voltage (Volts) versus capacity (Ah) versus discharge of a cell at two rates at room temperature before and after applying a circular bar crush. The figure shows that the performance of the cell was not affected by the crush test, further demonstrating the remarkable resistance of the cell technology to the occurrence of large-capacity dissipation internal short circuits when subjected to mechanical abuse.

Example 9

A 5Ah laminate packaged prismatic cell was prepared using the materials and methods of Example 1 but with the following differences.

The positive active material loading was 9.5 mg/cm ² , and the negative active material loading was 9.1 mg/cm ² . The individual cathode and anode pieces had an area of 141.9 cm ² and were assembled into a stack with 16 double side anode layers, and 15 double side cathode layers plus 2 single side cathode layers.

The battery of this embodiment has the following key elements.

a. A negative electrode comprising lithium titanium oxide (LTO) coated on an aluminum current collector. The coating is a mixture of LTO with a specific surface area of 10 m ² /g, acetylene black as conductive additive and PVdF as binder in a weight ratio of 90:3:7. The surface area of acetylene black is 100 m ² /g (Denka AB-100 from Denka) and the molecular weight of PVdF (Solef 5130 from Solvay) ranges from 1,000,000 to 1,200,000 mol/g. Acetylene black conductive carbon occupies less than 5% of the anode electrode surface. An uncoated aluminum strip forms the negative electrode tab.

b. A positive electrode comprising a high-nickel cathode material having _{an overall composition of Li 1.01} Mg _0.025 Ni _0.88 Co _0.12 Al _0.0064 O ₂ coated on an aluminum current collector. The coating is a mixture of acetylene black and PVdF in a weight ratio of 94:3:3. Acetylene black has a surface area of 100 m ² /g, and the molecular weight of PVdF ranges from 1,000,000 to 1,200,000 mol/g. An uncoated aluminum strip forms the anode tab.

c. A 21 μm thick polyolefin separator coated with alumina on one side and having a Gurley air permeability of 110 seconds, the alumina side being positioned opposite to the anode.

d. The geometric areas of the anode and cathode are the same.

e. An electrochemical cell was assembled using a stacked arrangement of a double-sided negative electrode, a separator, and a double-sided positive electrode.

f. The positive electrode tabs are superimposed and ultrasonically welded to each other and to the positive cell tab, and the negative electrode tabs are stacked to overlap each other and are stacked to be ultrasonically welded to each other and to the negative cell tab.

g. The end layer of the stack is the cathode.

h. _{An electrolyte comprising 1M LiPF 6} in a mixture of propylene carbonate, ethyl methyl carbonate and methyl butyrate in a weight ratio of 1:1:2, and having an ionic conductivity of 11 mS/cm at 25°C and 2 mS/cm at -40°C.

The performance of the battery was characterized by charging 2A charge, 8A discharge cycle between 2.65V and 1.5V at room temperature, followed by charging to 2.65V. Thereafter, the charged battery was subjected to a nail penetration test three times in the manner of Example 7, and then subjected to a crush test twice in the manner of Example 8. An array of three parallel green LEDs contacted across the ends of the cell remained lit for a total of five abuse trials. Thereafter, the performance of the abused battery was re-characterized by cycling 2A charge, 8A discharge cycles between 2.65V and 1.5V, and then continuously cycle the battery between 2.65V and 1.4V at a charge and discharge rate of 5A.

15 is a photograph of the cell after abuse testing with the lit LEDs still in contact across the ends of the cell, vividly showing the cell's remarkable misuse tolerance.

16 is a graph of voltage (volts) versus capacity (Ah) versus discharge of a cell from room temperature to 8 A before and after five abuse tests, showing that the performance of the cell is not affected by repeated mechanical abuse. .

17 is a graph of the discharge capacity versus number of cycles of a cell when subjected to 5 abuse tests and then cycled 5A/5A charge/discharge at room temperature in ambient atmosphere. The figure shows that the capacity delivered by the cell decreased during the first 5 days (50+ cycles), presumably because the electrolyte loses its volatile solvent components through holes in the packaging made due to nail penetration. The cell then cycled fairly stably at a capacity of about 4 Ah for nearly 3 weeks without further significant capacity loss until more than 300 cycles had elapsed, at which point the degradation in cell performance was probably through the nail holes in the packaging. This is due to the cumulative gradual infiltration of atmospheric moisture. These results indicate that the only impact of severe penetration and crush abuse on cell performance is due to packaging damage, further demonstrating the superior robustness of the cell technology of the present invention.

Although the terms “first,” “second,” “third,” and the like, may be used herein to describe various elements, components, regions, layers, and/or sections, such elements, components, regions, sides and /or the section should not be limited to the above terms. The term is used only to distinguish one element, component, region, layer or section from another element, component, region, layer or section. Thus, “a first element”, “component”, “region”, “layer” or “section” discussed below may be referred to as a second element, component, region, layer or section without departing from the teachings of the present invention. can

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. As used herein, the singular forms “a”, “an” and “the” are intended to include the plural forms including “at least one” unless the context dictates otherwise. "or" means "and/or". As used herein, the term “and/or” includes any and all combinations of one or more of the related listed items. The terms “comprises” and/or “comprising” or “includes” and/or “including,” as used herein, refer to the characteristic features referred to, Specifies the presence of a region, integer, step, operation, element, and/or component, but not the presence or addition of one or more other characteristic features, region, integer, step, operation, element, component, and/or group thereof. It will be further understood that there is no exclusion. The term “or a combination thereof” means a combination comprising at least one of the preceding elements.

Spatially relative terms such as "beneath", "below", "lower", "above", "upper )" and the like may be used herein for convenience of description to describe the relationship of one element or characteristic component to another element(s) or characteristic component(s) shown in the drawings. It will be understood that spatially relative terms are intended to encompass different orientations of the device in use or operation other than the orientation shown in the drawings. For example, when the device in the figures is turned over, elements described as “beneath” or “beneath” other elements or features face “above” the other elements or features. Thus, the exemplary term “below” can include both directions above and below. The device may otherwise be oriented (rotated 90 degrees or otherwise), and spatially relative descriptors used herein are to be interpreted accordingly.

Unless defined otherwise, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition, commonly used terms as defined in the dictionary are to be construed as having a meaning consistent with that in the context of the relevant art and this specification, and in an ideal or overly formal sense unless explicitly defined herein. It should be understood that it should not be interpreted in a negative sense.

Exemplary embodiments are described herein with reference to cross-sectional diagrams that are schematic diagrams of idealized embodiments. Accordingly, variations in the form of the examples, for example as a result of manufacturing techniques, are expected. Accordingly, the aspects described herein should not be construed as limiting to the specific shapes of the regions exemplified herein, but should include, for example, variations in shapes resulting from manufacturing. For example, regions shown or described as being flat may have a characteristic configuration that is rough and/or non-linear. Also, the sharp angles illustrated may be rounded. Accordingly, the regions illustrated in the drawings are schematic in nature, and the shapes thereof are not intended to illustrate the precise shape of the regions and are not intended to limit the scope of the claims of the present invention.

While this specification describes exemplary aspects, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the disclosed aspects. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the present invention without departing from the scope thereof. Accordingly, the invention is not intended to be limited to the particular embodiments disclosed as the best mode contemplated for carrying out the invention. It is also to be understood that the aspects disclosed herein are to be considered in an illustrative sense only and not in a limiting sense. A description of a characteristic feature, advantage, or aspect of each aspect is to be considered as applicable to the characteristic feature, advantage, or aspect of another similar aspect.

Various modifications of the invention in addition to those shown and described herein will be apparent to those skilled in the art from the foregoing description. Such modifications are also intended to fall within the scope of the appended claims.

Unless otherwise specified, it is understood that all reagents and components are available from sources known in the art.

The patents, publications and patent applications mentioned in the specification are indicative of the level of skill of those skilled in the art to which this invention pertains. These patents, publications, and patent applications are incorporated herein by reference to the same extent as if each individual patent, publication or patent application was specifically and individually incorporated herein by reference.

The foregoing description illustrates specific embodiments of the invention, but is not meant to limit the practice of the invention. The following claims are intended to define the scope of the invention including all equivalents thereof.

Claims (48)

A polycrystalline cathode comprising the formula Li _1+x MO _2+y (where -0.9≤x≤0.3, -0.3≤y≤0.3, and M contains 80 atomic% or more of Ni based on the total M) a cathode comprising an electrochemically active material, wherein the cathode electrochemically active material comprises a non-uniform distribution of Co; and
comprising an anode comprising an anode electrochemically active material of the formula Li _4+a Ti ₅ O _{12+b wherein -0.3≤a≤3.3 and -0.3≤b≤0.3;}
An electrochemical cell, wherein the anode and the cathode each independently comprise a current collector substrate comprising aluminum. The voltage to capacity profile of claim 1 , wherein the electrochemical cell exhibits a voltage to capacity profile that is substantially unchanged after puncturing with a blunt 2 mm diameter stainless steel nail at a rate of 1 cm/sec. which is an electrochemical cell. The electrochemical cell of claim 1 , wherein the electrochemical cell is characterized by substantially unchanged performance after subsequent storage for 33 months at 1,000 cycles and 0V conditions. The electrochemical cell of claim 1 , wherein after being cycled 1,000 times between 2.43V and 1.33V at a charge rate of 10C and a discharge rate of 10C in an oven at 45°C without external constraint, less than 10% An electrochemical cell, characterized by a 10C capacity reduction. The electrochemical cell of claim 1 , wherein the electrochemical cell is characterized by a capacity transfer of greater than 30% when discharged at 1.2V at a rate of 3.3C at minus 50°C. The electrochemical cell of claim 1 , which can be charged at a rate of at least 1C at minus 50°C. 7. The electrochemical cell of any one of claims 1-6, wherein the anode and the cathode are in a pouch cell. The electrochemical cell according to any one of claims 1 to 6, further comprising a separator comprising a ceramic, wherein the ceramic is in the form of a coating on a surface of the separator or a filler in the separator. The electrochemical cell of claim 8 , wherein the ceramic is a ceramic oxide, optionally aluminum oxide. The electrochemical cell of any one of claims 1 to 6, further comprising a separator comprising a porous polyolefin. The electrochemical cell of claim 1 , wherein the area ratio of the anode to the cathode is 1 or less, or the capacity ratio of the anode to the cathode is 1 or less, or both. The electrochemical cell of claim 1 , further comprising an electrolyte comprising a solvent and a salt. The electrochemical cell _{of claim 12 , wherein the electrolyte comprises a LiPF 6} salt in a mixture of propylene carbonate, ethyl methyl carbonate and methyl butyrate. 7. The electrochemical cell of any preceding claim, wherein the anode and the cathode comprise a PVdF binder. 7. The method according to any one of claims 1 to 6, wherein the cathode electrochemically active material comprises a plurality of crystallites and grain boundaries between the plurality of crystallites, wherein cobalt, aluminum or An electrochemical cell in which the concentration of both is higher than in the center of adjacent crystallites. The method according to any one of claims 1 to 6, wherein _{M in the formula Li 1+x} MO _2+y is Mg, Sr, Co, Al, Ca, Cu, Zn, Mn, V, Ba, Zr, Ti An electrochemical cell comprising Ni and at least one metal selected from the group consisting of , Cr, Fe, Mo, B, and any combination thereof. The electrochemical cell according to claim 1 , wherein the cathode electrochemically active material comprises Ni and at least one of Mg, Co or Al. Cathode electrochemical comprising the formula Li _1+x MO _2+y (where -0.9≤x≤0.3, -0.3≤y≤0.3, and M contains 80 atomic% or more of Ni based on the total M) A cathode comprising an active polycrystalline material, wherein the cathode electrochemically active material comprises a plurality of crystallites and grain boundaries between the plurality of crystallites, wherein the concentration of cobalt, aluminum, or both of the grain boundaries is adjacent. higher than at the center of the crystallites, the cathode;
at least two anodes comprising an anode electrochemically active material of the formula Li _4+a Ti ₅ O _{12+b, wherein -0.3≤a≤3.3 and -0.3≤b≤0.3;}
a porous polyolefin separator and
an electrolyte comprising a lithium salt and a carbonate solvent;
An electrochemical pouch cell comprising:
the anode and the cathode independently further comprise a PVdF binder admixed with each of the anode electrochemically active material and the cathode electrochemically active material,
The anode and the cathode each independently further include a current collector substrate comprising aluminum, the cathode current collector being coated on both sides with individual electrochemically active materials,
the two or more anodes are the end layers of the stack of electrodes;
An electrochemical pouch cell, wherein the area ratio of the anode to the cathode is less than or equal to one, or the capacity ratio of the anode to the cathode is less than one. 19. The electrochemical cell of claim 18, wherein the electrochemical cell is characterized by a substantially unchanged voltage versus capacity profile after puncturing with a blunt 2 mm diameter stainless steel nail at a rate of 1 cm/sec. 19. The electrochemical cell of claim 18, wherein the electrochemical cell is characterized by performance substantially unchanged after subsequent storage for 33 months at 1,000 cycles and 0V conditions. 19. The 10C capacity reduction of claim 18, wherein the unconstrained electrochemical cell is cycled 1,000 times between 2.43V and 1.33V at a charge rate of 10C and a discharge rate of 10C in a 45°C oven. characterized in that, the electrochemical cell. 19. The electrochemical cell of claim 18, wherein the electrochemical cell is characterized by a capacity transfer of greater than 40% when discharged to 1.2V at -50°C at a rate of 3.3C and charged at -50°C at a rate of 1C. battery. 23. The electrochemical cell according to any one of claims 18 to 22, wherein the separator comprises a ceramic, wherein the ceramic is in the form of a coating on a surface of the separator or a filler in the separator. 24. The electrochemical cell of claim 23, wherein the ceramic is a ceramic oxide, optionally aluminum oxide. 23. The method according to any one of claims 18 to 22, wherein _{M in formula Li 1+x} MO _2+y is Mg, Sr, Co, Al, Ca, Cu, Zn, Mn, V, Ba, Zr, Ti, An electrochemical cell comprising Ni and at least one metal selected from the group consisting of Cr, Fe, Mo, B, and any combination thereof. 23. The electrochemical cell of any one of claims 18-22, wherein the cathode electrochemically active material comprises Ni and at least one of Mg, Co or Al. 23. Electricity according to any one of claims 18 to 22, wherein the cathode active material comprises Co in a concentration gradient within the crystallites or secondary particles, the concentration of Co being greater at the surface of the particle than at the center. chemical cell. 23. The electrochemical cell according to any one of claims 18 to 22, wherein the Co is present in the coating on the polycrystalline particle at a higher concentration than in the core of the secondary particle. 23. The electrochemical cell of any one of claims 18-22, wherein the separator is a polyolefin separator further comprising a ceramic coating on at least one side of the separator, wherein the ceramic is optionally aluminum oxide. An electrochemical cell according to any one of claims 18 to 29 in combination. 18. An electrochemical cell according to any one of claims 1 to 17 in combination. 30. The electrochemical pouch cell of any preceding claim, wherein the cathode active material comprises Li, Ni, Co, Al and Mg. 33. The electrochemical cell of claim 32, wherein Ni is present at at least 85 at% based on total M. _{The electrochemical cell} of claim 32 , wherein the cathode comprises Li _1.01 Mg _0.025 Ni _0.88 Co _0.12 Al 0.0064 O ₂ , and the anode comprises Li ₄ Ti ₅ O ₁₂ and has a specific surface area of 10 mVg. 33. The electrochemical cell of claim 32, wherein the anode, the cathode, or both further comprise conductive carbon. 36. The electrochemical cell of claim 35, wherein the conductive carbon comprises acetylene black. 37. The electrochemical cell of claim 36, wherein the acetylene black has a surface area of about 100 m ² /g. 33. The electrochemical cell of claim 32, wherein the anode, the cathode or both comprise a PVdF binder having a molecular weight in the range of 1,000,000 to 1,200,000 mol/g. The electrochemical cell of claim 32 , comprising a separator, the separator coated on one side with aluminum oxide, the separator disposed in the electrochemical cell such that the aluminum oxide is proximate to the cathode. 33. The electrochemical cell of claim 32, wherein the electrolyte has an ionic conductivity of about 11 mS/cm at 25°C and 2 mS/cm at -40°C. 33. The electrochemical cell of claim 32, comprising a state of charge to a voltage of about 1.4V or less, optionally about 0.1V, optionally about 0V, optionally less than 0V. 33. The electrochemical cell of claim 32, wherein the anode electrochemically active material has a specific surface area of 4 to 20 m ² /g, optionally 7 to 13 m ² /g. 33. The electrochemical cell of claim 32, wherein the anode electrochemically active material has a particle size of from about 0.1 to about 100 microns, optionally from about 1 to about 10 microns. 33. The electrochemical cell of claim 32, wherein the anode electrochemically active material has an electrochemical redox potential for lithium of about 1.55V. 33. The anode active material of claim 32, wherein the anode active material comprises Li _3+z Ti _6-z O ₁₂ , wherein 0≤z≤1, optionally 0≤z≤1, optionally 0.1≤z≤0.8 or optionally 0≤z≤0.5, an electrochemical cell. 33. The electrochemical according to claim 32, wherein the anode active material has the formula Li _4+y Ti ₅ O ₁₂ , wherein 0≤y≤3, optionally 0.1≤y≤2.8 or optionally 0≤y≤2.6. battery. An electrochemical cell substantially as described herein. An electrochemical cell substantially as described herein at a voltage of 1.4V or less, optionally 0.1V or less, optionally 0V or less.

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