KR20210046684A - Lithium ion battery - Google Patents

Abstract

A multi-core lithium ion battery includes a hermetically sealed sealant and a support member disposed within the hermetically sealed sealant. The support member includes a plurality of cavities and a plurality of lithium ion core members disposed in the plurality of cavities. The battery further includes a plurality of cavity liners, each cavity liner positioned between a corresponding one of the lithium ion core members and a corresponding one of the cavities on the surface.

Description

Lithium ion battery

Cross-reference of related applications

This application claims the benefit of the priority of "Lithium Ion Battery" of a regular patent application invention filed on July 30, 2018 and assigned the number 16/048,874. The above U.S. regular patent application is incorporated herein by reference in its entirety.

Field of invention

The present invention relates to a lithium ion battery, and more particularly to a multi-core lithium ion battery with improved safety and reduced manufacturing cost.

Demand for electro-chemical cells, such as lithium-ion batteries, is in applications such as electric vehicles and grid storage systems, and other multi-cell battery applications such as electric bikes, non-disruptive power battery systems, and lead acid replacement. It continues to increase due to the growth of the battery. Higher energy and power densities are requirements for these applications, but if not more important than that, low-cost manufacturing and improved safety requirements to enable widespread commercial adoption are important. In addition, the energy-to-power ratio of these batteries needs to be tailored to the application.

Large applications such as grid storage and electric vehicles require multiple cells connected in series and parallel arrays. Suppliers of batteries focus on large cells, defined herein as >10 Ah (in amperes), for each single cell, or small cells as defined herein as less than 10 Ah. Large cells, such as prismatic or polymer cells with stacked electrodes, are made by LG Chemical, AESC, ATL and other manufacturers. Small cells, such as 18650 or 26650 cylindrical cells, or prismatic cells, such as 183765 or 103450 cells and other similarly sized cells are Sanyo, Panasonic, EoneMoli, Boston-Power, Johnson Controls, Saft, BYD, Gold Peak Made by the back These small cells often use an oblong or cylindrical jelly roll structure. Some small cells are polymer cells with stacked electrodes that are similar to large cells, but with less capacity.

Existing small and large cell batteries have several important drawbacks. Small cells, such as 18650 cells, generally have the disadvantage of being limited by the sealant or'can', which leads to limitations in cycle life and calendar life, in part due to mechanical stress or lack of electrolyte. When the lithium-ion battery is charged, the electrode expands. Because of the can, the jelly roll structure of the electrode is limited and mechanical stress occurs in the jelly roll structure, thereby limiting the life cycle. As more and more storage capacity is required, more active anode and cathode materials are inserted into a given volume of can, which creates additional mechanical stress on the electrode.

In addition, the ability of small cells to increase the amount of electrolyte is limited and as lithium is intercalated and de-intercalated, electrode movement compresses the electrolyte from the jelly roll. As a result, the electrolyte is depleted in the electrode, and a concentration gradient of lithium ions and dehydration of the electrode occur while power is consumed, resulting in a dry area that blocks side reactions and ion pathways and reduces battery life. To overcome these problems, especially for long-life batteries, users must compromise performance by lowering the state of charge, limiting the available capacity of the cell, or lowering the charging rate.

On the mechanical side, small cells are difficult and expensive to assemble into large arrays. Complex welding patterns must be created to minimize the possibility of welding errors. Welding errors lead to capacity degradation and potential heat generation at the wrong weld joint. The more cells there are in the array, the higher the risk of errors and the lower the manufacturing yield. This means higher product and warranty costs. There are potential safety issues in the packaging of small cells, as well as fault problems of welding and internal shorts. Proper packaging of small cells is required to prevent continuous thermal runaway due to failure of one cell. Such packaging increases the cost.

In the case of large batteries, the disadvantages are primarily safety, low volume and gravimetric capacity, and expensive manufacturing methods. Large cells with large area electrodes have a lower manufacturing yield compared to small cells. If the large battery electrode is defective, more material is wasted and the overall yield is low compared to manufacturing a small battery. A 50Ah battery compared to a 5Ah battery can be considered as an example. Even if defects for both production methods occur only every 50 Ah of the cells produced, a defect in a 50Ah cell can result in a material loss of 10 times compared to a 5Ah cell.

Another issue with large batteries is safety. The energy released by a cell entering thermal runaway is proportional to the amount of electrolyte in the cell that is accessible during a thermal runaway scenario. The larger the cell, the more free space available for the electrolyte to fully saturate the electrode structure. Since the amount of electrolyte per Wh for large cells is generally higher than for small cells, large cell batteries are generally less secure as they are more powerful systems during thermal runaway. Of course, all thermal runaways will depend on the specific scenario, but the more fuel (electrolyte) there is, the stronger the fire will be in case of a catastrophic event. In addition, when a large battery enters the thermal runaway mode, the heat generated by the battery causes a thermal runaway reaction in the adjacent battery, causing serious destruction of the pack and surrounding facilities, as well as the continuous effect of igniting the entire pack and unsafe for users. Causes the condition.

When comparing the performance parameters of small cells and large cells, it can be seen that small cells generally have higher gravimetric (Wh/kg) and volumetric (Wh/L) capacities when compared to large cells. Compared to large cells, it is easier to group a plurality of small cells by using binning techniques for capacity and impedance to match the overall distribution of production runs in a more efficient manner. This leads to higher manufacturing yields during mass production of the battery pack, and also the continuous runaway reaction of the battery pack due to ignition (one of the most common problems in the field of safety issues), e.g. by ignition by an internal short circuit in one cell. It is easier to arrange the small cells into a volume efficient array that limits the. In addition, there is a cost advantage of using a small battery because the production method is well established in the industry with high yield and the failure rate is low. The machine was readily available and costs were incurred outside the manufacturing system.

On the other hand, the advantage of large cells is that there is often room for a common electromechanical connector that is easy to use, and obviously less, which allows efficient pack manufacturing without having to solve many problems and the know-how required to assemble an array of small cells. Ease of assembly for battery pack OEMs that can suffer from a more robust large format structure with a number of cells.

Compared to large cells, with better safety and lower manufacturing cost, in order to take advantage of the advantages of using small cells to make batteries of larger size and higher power/energy capacity, with a multi-core (MC) cell structure. The assembly of small-sized batteries was developed.

One of these MC cell structures developed by BYD Company Ltd. uses an array of MCs that are integrated into a single container made of metal (aluminum, copper alloy or nickel chromium). This array is described in the following documents: EP 1952475 A0, WO2007/053990, US2009/0142658 A1, CN 1964126A. Since the BYD structure has only the metal material surrounding the MC, it has a disadvantage that a sharp object penetrates the core and causes a local short circuit in case of mechanical impact. Since all the cores are in a common container (not individual cans) where electrolyte is shared between the cores, any individual failures due to manufacturing defects or external misuse can propagate to other cores and possibly destroy the MC structure. These batteries are not safe.

A method of preventing thermal runaway in the assembly of a plurality of electrochemical cells is described in US2012/0003508 A1. In the MC structure described in this patent application, individual cells are connected in parallel or in series, and each cell has a jelly roll structure contained in its own can. These individual cells are then inserted into a container filled with rigid foam containing flame retardant additives. These safety measures are expensive to create and limit energy density, in part due to the excessive cost of mitigating materials.

Another MC structure is described in patent applications US2010/0190081 A1 and WO2007/145441 A1, wherein the use of two or more stacked secondary batteries having a plurality of cells providing two or more voltages by a single battery is disclosed. In this arrangement, single cells are connected in series in the seal using a separator. Series elements only make higher voltage cells, but do not solve any safety or cost issues compared to regular stacked single voltage cells.

Although this MC type battery offers certain advantages over large cell batteries, it still has certain disadvantages in terms of safety and cost.

The present invention is a novel type of MC with reduced production costs and improved safety while providing the advantages of larger sized batteries, such as the convenience of assembly of such an array of batteries and the ability to customize the power-to-energy ratio. Provides a lithium-ion battery structure.

A multi-core lithium ion battery having a hermetically sealed material having a support member disposed within the hermetically sealed material is described. The support member may include a plurality of cavities and a plurality of lithium ion core members disposed within a corresponding one of the plurality of cavities. There are a plurality of cavity liners, each cavity liner positioned between a corresponding one of the lithium ion core members and a surface of a corresponding one of the cavities. The support member includes a kinetic energy absorbing material and the kinetic energy absorbing material is formed of one of aluminum foam, ceramic and plastic. The cavity liner is formed of a plastic material and a plurality of cavity liners are formed as part of the monolithic liner member. An electrolyte contained in each core is further included, and the electrolyte includes at least one of a flame retardant, a gas generating agent, and a redox carrier. Each lithium ion core member includes an anode, a cathode, and a separator disposed between each anode and the cathode. An electrical connector is also included in the sealing material that electrically connects the core member to an electrical terminal outside the sealed sealing material. The electrical connector includes two bus bars, a first bus bar interconnecting the anode of the core member to a negative terminal member of a terminal outside the sealing material, and a second bus bar connecting the cathode of the core member to the outside of the sealing material. Both terminals of the terminals are interconnected by means of terminal members.

In addition, at least one of the sealant and support member may be an insulating mineral material (e.g., AFB® material, Cavityrock® material, ComfortBatt® material and FabrockTM material (Rockwool Group, Hedefusene, Denmark); Promafour® material, Microtherm® material ( Promat Inc. of Tisselt, Belgium); and from Calcium-magnesium-silicate wool from Morgan Thermal Ceramics (Birkenhead, UK). The insulating mineral material can be used as a composite and includes a fiber and/or powder matrix. The mineral matrix material may be selected from the group comprising alkaline earth silicate wool, basalt fiber, asbestos, volcanic glass fiber, glass fiber, cellular glass, and any combination thereof. The mineral material may include, but not necessarily, a binding material. The disclosed bonding material may be a polymeric material and may be selected from the group comprising nylon, polyvinyl chloride ("PVC"), polyvinyl alcohol ("PVA"), acrylic polymer, and any combination thereof. The mineral material may further contain flame retardant additives, but this is not essential, and an example of such a material is alumina trihydrate ("ATH"). Mineral materials can be produced in a variety of media, such as rolls, sheets and boards, and can be rigid or flexible. For example, the material may be a pressed and compressed block/board or may be a plurality of woven fibers that are spongy and compressible.

In another aspect of the invention, the core members are connected in parallel or connected in series. Alternatively, the first set of core members is connected in parallel and the second set of core members is connected in parallel, and the first set of core members is connected in series with the second set of core members. The support member has the form of a honeycomb structure. The kinetic energy absorbing material includes a compressible medium. The sealant includes a wall with compressible elements that create an electrical short in the lithium ion battery when compressed due to a force applied to the wall. The cavities in the support member and their corresponding core members are one of a cylindrical shape, an oblong shape, and a prismatic shape. At least one of the cavity and its corresponding core member has a different shape from the other cavity and its corresponding core member.

In another aspect of the present invention, at least one of the core members has high power characteristics and at least one of the core members has high energy characteristics. The anode of the core member is formed of the same material, and the cathode of the core member is formed of the same material. Each separator member includes a ceramic coating and each anode and each cathode includes a ceramic coating. At least one of the core members includes one of an anode and a cathode having a thickness different from that of the anode and cathode of the other core member. At least one cathode comprises at least two of the compounds A to M groups of the material. Each cathode contains a surface modifier. Each anode comprises either Li metal or carbon and graphite. Each anode contains Si. Each core member includes a wound anode, a cathode, and a separator structure, or includes an anode, a cathode, and a separator structure in which each core member is stacked.

In another aspect of the invention, the core member has substantially the same electrical capacity. At least one of the core members has a different electric capacity than the other core members. At least one of the core members is optimized for power storage and at least one of the core members is optimized for energy storage. A tab for electrically connecting each anode to the first bus bar and a tab for electrically connecting each cathode to the second bus bar are further included, wherein each tab opens each tab when the specified current is exceeded. And means for stopping the flow of electrical current through it. The first bus bar includes a fuse element proximate to each interconnection point between the anodes of the first bus bar, and the second bus bar includes a fuse element proximate to each interconnection point between the cathodes of the second bus bar. So it stops the flow of electric current from the melting element when the specified current is exceeded. A protective sleeve surrounding each core member is further included, and each protective sleeve is disposed outside the cavity containing its corresponding core member.

In another aspect of the present disclosure, a sensing wire is electrically interconnected with the core member and is configured to enable electrical monitoring and balancing of the core member. The sealed sealing material includes a flame-retardant member and the flame-retardant member includes a flame-retardant mesh material attached to the outside of the sealing material.

In yet another embodiment, a multi-core lithium ion battery is described that includes a hermetic sealant. A support member is disposed within the hermetic seal, the support member comprising a plurality of cavities, wherein the support member comprises a kinetic energy absorbing material. There are a plurality of lithium ion core members disposed within a corresponding one of the plurality of cavities. A plurality of cavity liners are further included, each cavity liner positioned between a corresponding one of the lithium ion core members and a surface of a corresponding one of the cavities. The cavity liner is formed of a plastic material and a plurality of cavity liners are formed as part of the monolithic liner member. The kinetic energy absorbing material is formed of one of aluminum foam, ceramic and plastic.

In another aspect of the invention, there is an electrolyte contained in each of the cores and the electrolyte comprises at least one of a flame retardant, a gas generating agent, and a redox carrier. Each lithium ion core member includes an anode, a cathode, and a separator disposed between each anode and the cathode. An electrical connector is also included in the sealing material that electrically connects the core member to an electrical terminal outside the sealed sealing material. The electrical connector includes two bus bars, a first bus bar interconnecting the anode of the core member to a negative terminal member of a terminal outside the sealing material, and a second bus bar connecting the cathode of the core member to the outside of the sealing material. Both terminals of the terminals are interconnected by means of terminal members. The core members are connected in parallel. The core members are connected in series. The lithium ion battery may include a first set of core members connected in parallel and a second set of core members connected in parallel, wherein the first set of core members is connected in series with the second set of core members.

In another aspect, the support member has the form of a honeycomb structure. The kinetic energy absorbing material includes a compressible medium. The lithium sealant includes a wall with compressible elements that create an electrical short in a lithium ion battery when compressed due to a force applied to the wall. The cavities in the support member and their corresponding core members are one of a cylindrical shape, an oblong shape, and a prismatic shape. At least one of the cavity and its corresponding core member has a different shape from the other cavity and its corresponding core member. At least one of the core members has high power characteristics, and at least one of the core members has high energy characteristics. The anode of the core member is formed of the same material, and the cathode of the core member is formed of the same material. Each separator member includes a ceramic coating. Each anode and each cathode comprise a ceramic coating. At least one of the core members includes one of an anode and a cathode having a thickness different from that of the anode and cathode of the other core member.

In another embodiment, at least one cathode comprises at least two of the compound A-M groups of the material. Each cathode contains a surface modifier. Each anode comprises Li metal, carbon, graphite or Si. Each core member includes a wound anode, cathode and separator structure. Each core member includes a stacked anode, cathode, and separator structure. The core member has substantially the same electrical capacity. At least one of the core members has a different electric capacity than the other core members. At least one of the core members is optimized for power storage and at least one of the core members is optimized for energy storage.

In another aspect of the present invention, a tab for electrically connecting each anode to the first bus bar and a tab for electrically connecting each cathode to the second bus bar are further included, wherein each tab comprises a specified current And means for stopping the flow of electrical current through each tap when is exceeded. The first bus bar may include a fuse element proximate to each interconnection point between anodes of the first bus bar and a fuse element proximate to each interconnection point between cathodes of the second bus bar. When exceeded, the flow of electric current from the melting element is stopped. A protective sleeve surrounding each core member is further included, and each protective sleeve is disposed outside the cavity containing its corresponding core member.

In another embodiment of the present invention, a sensing wire is electrically interconnected with the core member and is configured to enable electrical monitoring and balancing of the core member. The sealed sealing material includes a flame-retardant member and the flame-retardant member includes a flame-retardant mesh material attached to the outside of the sealing material.

In yet another embodiment, a multi-core lithium ion battery comprising a hermetic sealant is described with a lithium ion cell region and a shared atmosphere region inside the sealant. There is a support member disposed within the region of the lithium ion battery of the hermetically sealed material, and the support member includes a plurality of cavities, each cavity having an end open to the shared atmosphere region. A plurality of lithium ion core members are present, and each lithium ion core member has an anode and a cathode disposed in a corresponding cavity among the plurality of cavities, and the anode and the cathode are exposed to a shared atmosphere region by an open end of the cavity. And the anode and the cathode are substantially surrounded by a cavity along their length. The support member includes a kinetic energy absorbing material. The kinetic energy absorbing material is formed of one of aluminum foam, ceramic and plastic.

In another aspect, there are a plurality of cavity liners, each cavity liner being positioned between a corresponding one of the lithium ion core members and a corresponding one of the cavities and the cavity liner formed of a plastic material. A plurality of cavity liners are formed as part of the monolithic liner member. An electrolyte contained in each core is present and the electrolyte includes at least one of a flame retardant, a gas generating agent, and a redox carrier. Each lithium ion core member includes an anode, a cathode, and a separator disposed between each anode and the cathode. An electrical connector is included in the sealing material that electrically connects the core member to an electrical terminal outside the sealed sealing material. The electrical connector includes two bus bars, a first bus bar interconnecting the anode of the core member to a negative terminal member of a terminal outside the sealing material, and a second bus bar connecting the cathode of the core member to the outside of the sealing material. Both terminals of the terminals are interconnected by means of terminal members.

In another aspect of the invention, the core members are connected in parallel or the core members are connected in series. Alternatively, the first set of core members is connected in parallel and the second set of core members is connected in parallel, and the first set of core members is connected in series with the second set of core members.

In another embodiment, a lithium ion battery is described and includes a sealed sealant and at least one lithium ion core member disposed within the sealed sealant. The lithium ion core member includes an anode and a cathode, and the cathode includes at least two compounds selected from the group of compounds A to M. There is only one lithium ion core member. The hermetic seal is a polymer bag or the hermetic seal is a metal canister. Each cathode includes at least two compounds selected from the group of compounds B, C, D, E, F, G, L and M, and may further include a surface modifier. Each cathode comprises at least two compounds selected from the group of compounds B, D, F, G, and L. The battery charges to voltages higher than 4.2V. Each anode comprises one of carbon and graphite. Each anode contains Si.

In yet another embodiment, a lithium ion battery is described as including a sealed sealant and at least one lithium ion core member disposed within the sealed sealant. The lithium ion core member includes an anode and a cathode. An electrical connector in the seal electrically connects at least one core member to an electrical terminal outside the sealed seal, and the electrical connector comprises means for stopping the flow of electrical current through the electrical connector when a specified current is exceeded. . The electrical connector includes two bus bars, a first bus bar interconnecting the anode of the core member to a negative terminal member of a terminal outside the sealing material, and a second bus bar connecting the cathode of the core member to the outside of the sealing material. Both terminals of the terminals are interconnected by means of terminal members. The electrical connector further comprises a tab for electrically connecting each anode to the first bus bar and a tab for electrically connecting each cathode to the second bus bar, wherein each tab is each And means for stopping the flow of electric current through the tap of the. In the electrical connector, the first bus bar includes a fuse element close to each interconnection point between the anodes of the first bus bar, and the second bus bar is a fuse element close to each interconnection point between the cathodes of the second bus bar. It may include stopping the flow of electric current from the melting element when the specified current is exceeded.

The invention will be better understood upon reading the following description, which has been referred to the drawings and is provided as a non-limiting example.
1A is an exploded perspective view of a multi-core, lithium-ion battery according to the present invention.
1B is a cross-sectional view of a multi-core, lithium-ion battery according to the present invention.
1C is a stress-strain plot of an exemplary energy absorbing material of a support member according to the present invention.
1D is a cross-sectional view of another embodiment of a multi-core, lithium-ion battery according to the present invention.
2 is a plan view of a configuration of a plurality of support members according to the present invention.
3 is a perspective view of another embodiment of a multi-core, lithium-ion battery according to the present invention.
4 is a perspective view of another embodiment of a support member having a mixed oblong and cylindrical cavity according to the present invention.
5 is a perspective view of a core member stacked and wound up of a prism according to the present invention.
Figure 6a shows a parallel/series connected MC lithium ion battery according to the present invention.
6B is a perspective view of a parallel/series connected MC lithium ion battery according to the present invention.
7A is a cross-sectional view of an egg-boxed wall of the sealing material according to the present invention.
Fig. 7b is a cross-sectional view of an egg-boxed wall of a sealant according to the invention during mechanical impact on the wall.

In FIGS. 1A and 1B, there is a multi-core (MC) array 100 of lithium ion core members 102a-j having a jelly roll core structure and a cylindrical shape. Various shapes and sizes of ionic core members can be used in connection with the present invention and specific shapes and sizes are described below. There is a set of electrically conductive tabs 104 connected to the cathode of each core member 102a-j and a set of electrically conductive tabs 106 connected to the anode of each core member 102a-j. The tab 104 is also connected to the cathode bus bar 108 and the tab 106 is connected to the anode bus bar 110. Cathode tab 104 and anode tab 106 are welded to bus bars 108 and 110 using spot welding or laser welding techniques. The bus bars 108 and 110 are interconnected to the positive terminal 112 and the negative terminal 114 on the exterior of the MC sealant 116. In this configuration, all of the ion core members 102a-j are connected in parallel, but may be connected in series or in other configurations that will be apparent to those skilled in the art.

The MC sealing material 116 of Fig. 1B is hermetically sealed. The support structure 120, which may be a part of the sealing material 116 or a separate part, is configured so that the ion core member can be accommodated at an appropriate separation interval, and limited expansion occurs during the charging and discharging reactions, and thus individual ion core members It can be made to prevent the mechanical interaction of the. Preferably, the sealing material 116 may be made of a plastic or ceramic material, or may be made of a metal. If metal is used, exposed steel is undesirable and any steel container will need to be coated with an inert metal such as nickel. Preferred metals are aluminum, nickel or other inert metals depending on the chemical substance used. Many types of plastics and ceramics are possible as long as they are inert to chemical and electrochemical environments. Examples of plastics and ceramics are polypropylene, polyethylene, alumina, and zirconia. The sealant 116 may include a flame retardant mesh attached to the outside of the sealant to prevent fire from reaching the inside of the sealant.

In the encapsulant 116 is an electrically insulating support member 120, which may be made of ceramic, plastic, such as polypropylene, polyethylene, or other material such as aluminum foam, in the lithium ion core region 118. The support member 120 must be sufficiently deformed/compressed to protect the core member from damage when an impact occurs. In addition, by dissipating heat during battery charging and discharging, creating a uniform temperature distribution, and dissipating heat during an internal short circuit that causes catastrophic failure, e.g., thermal runaway of one core member, the thermal conductivity is tailored to the application. It is desirable to lose. Proper heat dissipation properties will limit the possibility of continuous thermal runaway between the cores. The support member can also absorb the electrolyte, which can be trapped within the support member if the electrolyte is discharged during misuse of the core member.

In addition, at least one of the sealing material 116 and the support member 120 is an insulating mineral material (e.g., AFB® material, Cavityrock® material, ComfortBatt® material, and FabrockTM material (Rockwool Group, Hedefusene, Denmark); Promafour® Materials, Microtherm® materials (Promat Inc., Tisselt, Belgium); and calcium-magnesium-silicate wool products from Morgan Thermal Ceramics of Birkenhead, UK. The insulating mineral material can be used as a composite and includes a fiber and/or powder matrix. The mineral matrix material may be selected from the group comprising alkaline earth silicate wool, basalt fiber, asbestos, volcanic glass fiber, glass fiber, cellular glass, and any combination thereof. The mineral material may include, but not necessarily, a binding material. The disclosed bonding material may be a polymeric material and may be selected from the group comprising nylon, polyvinyl chloride ("PVC"), polyvinyl alcohol ("PVA"), acrylic polymer, and any combination thereof. The mineral material may further contain flame retardant additives, but this is not essential, and an example of such a material is alumina trihydrate ("ATH"). Mineral materials can be produced in a variety of media, such as rolls, sheets and boards, and can be rigid or flexible. For example, the material may be a pressed and compressed block/board or may be a plurality of woven fibers that are spongy and compressible.

A deformable kinetic energy absorbing support member 120 is particularly preferred, because it reduces the amount of local deformation in each core member 102a-j by distributing the impact load over a wider area, thereby lowering the likelihood of an electrical short. Because there is. Examples of kinetic energy absorbing materials are foams, such as aluminum foam, plastic foam, porous ceramic structures, honeycomb structures or other open structures, fiber-filled resins and phenolic materials. Examples of fiber fillers for plastic and resin materials are glass fibers or carbon fibers. Examples of aluminum containing energy absorbers are aluminum foams with open or closed pores, aluminum honeycomb structures, and engineered materials such as Altucore™ and CrashLite™ materials. It is important that the core is protected from penetration as much as possible to prevent mechanically induced short circuits inside when the support member collapses during impact, collision or other mechanical misuse. This makes the structure more secure.

Energy absorbers are generally a type of material that absorbs kinetic mechanical energy by compressing, deflecting, and not repulsing with a relatively constant stress over a long distance. Springs perform somewhat similar functions, but are repellent, so they are energy storage devices rather than energy absorbers. If the applied stress exceeds the “impact stabilizer” of the kinetic energy absorber material, reference 150 in FIG. 1C, the energy absorber will begin to compress at a fairly constant stress, up to about 50-70% of the strain of the material. This extended section of stress/strain defines the behavior of the ideal energy absorber. In this region, the area under the curve represents the product of stress x strain, ie "work." In an actual block of finite sized energy absorber material, such as support member 120, this would be represented as:

Force X displacement

In other words,

Force (pounds) x Displacement (feet) = work (feet pounds)

And

Work (feet pounds) = Kinetic energy (feet pounds)

What is to be done to compress the support member 120 is equal to the kinetic energy of the mass that can affect the support member 120. As will be apparent to those skilled in the art, when designed with an appropriate thickness and compressive strength, the support member 120 absorbs kinetic energy that can absorb all the kinetic energy of the impact on the battery, for example, in the event of a collision of an electric vehicle. It can be made of materials. The most important point is that the load in the support member 120, that is, the lithium ion core members 102a-j, does not feel any force greater than the impact strength of the material (defined below). Therefore, by absorbing the energy of the impact mass over a controlled distance with a constant force, the structure to be protected, that is, the lithium ion core member 102a-j, is a fatal result that may occur when the mass directly collides with the structure. There will be no need to withstand concentrated high energy/high force shocks that will be generated with.

When a load is applied to a structure made of energy absorbing material, it will yield the equation flexibly according to the Young's modulus. However, at a strain of approximately 4-6%, i.e. at 152 in FIG. 1C, in this particular example of the Al foam, depending on the structure size, it will continue to crush and collapse at a relatively constant stress. Depending on the initial relative density of the material, this constant collapse, for this Al foam material, will proceed to a strain of approximately 50-70%, i.e., (154) in FIG. 1C. At this point, when the energy absorbing material enters a "densification" state, the stress/parallel factor curve will begin to rise. The point on the stress/strain curve at which a material transitions from an elastically deformed state to a plastically deformed state defines the "impact strength" of a material.

The relatively flat long section of the curve between the 4-6% transition and the strain of 50-70% (including approximately 45-65% of the possible strain values of the material) is referred to as the "crush plateau". This unique property of kinetic energy absorbing materials protects the load, making them useful for absorbing the kinetic energy of the collision mass.

To further protect the core member, a cylindrical material made of metal, ceramic or plastic may be added around the core structure as sleeve 121 of FIG. 1A. This sleeve may be added around the individual core, directly to the outer yarn of the liner material, or applied to the interior of the cavity structure in the support member. This prevents sharp objects from penetrating the core. Although only one sleeve is shown in the figures, it will be apparent that sleeves will be included in each core member.

Alternatively, the support member 120 may be designed to have an open area 160 containing the filling material 162, as shown in FIG. 1D. Examples of filling materials include irregular or regular shaped media, which can be hollow or dense. Examples of hollow media are metal, ceramic or plastic spheres which are compressible at various pressures and have the purpose of functioning as an energy absorber for collision avoidance. Specific examples are aluminum hollow spheres, ceramic grinding media of alumina or zirconia, and polymer hollow spheres.

The support member 120 may also be optimized to rapidly transfer heat throughout the support member and distribute it evenly throughout the battery or to limit heat exposure between cores if one core undergoes thermal runaway during misuse. In addition to increasing safety, this will limit the maximum operating temperature to extend battery life and cause the battery to lose thermal management or be passive. Most importantly, the thermal properties of the support member 120 help prevent failure propagation from a failed core member to another core member because of the material's optimized heat transfer properties and ability to impede flame propagation. Because the material is also absorbent, it can absorb the leaked electrolyte into the material, which can help to reduce the severity of catastrophic failures.

a) enables the distribution of the ion core members 102a-j to optimize the battery for both safety and high energy density, b) enables cooling while simultaneously enabling rapid heat propagation of the ion core members 102a-j And, c) providing a protective collision-absorbing structure for ion core members 102a-j and reactive chemicals, and d) using a widely recognized fire protection material through flame arrest, the support member 120 Increases the overall safety of the MC battery.

A cylindrical cavity 122 is formed in the support member 120 for receiving the lithium ion core members 102a-i, and there is one core per cavity. In this configuration, the cylindrical cavity 122 has an opening 126 having a diameter slightly larger than that of the lithium ion core member 102. The opening 126 faces and is exposed to the shared atmosphere area 128 in the sealant 116. Without individual smaller seals (eg, cans or polymer bags that provide a hermetic seal between the active core members), the anode/cathode of the core member is directly exposed to the shared atmosphere region 128. Eliminating the canned core member not only reduces manufacturing costs, but also improves safety. In case of failure of the core member and resulting fire, the exhausted gas can occupy the shared atmosphere area 128, which provides significantly more space than would be possible with a typical individual'canned' core member. If the pressure of the canned core member accumulates, the probability of explosion is greater than in the present invention, which provides more volume for the gas to occupy, thereby reducing pressure build-up. In addition, the can generally ruptures at a much higher pressure than the inventive structure resulting in a mild failure mode in the case of the present invention.

Within each cavity 122 is a thin cavity liner 124 positioned between the support member 120 and the ion core members 102a-i. In general, all of the cavity liners (in this case the number of cavities corresponds to 10) are formed as part of the monolithic cavity liner member 124'. The liner is preferably made of polypropylene, polyethylene or any other plastic that is chemically inert to the electrolyte. Liners can also be made of ceramic or metallic materials, but they are expensive and are not preferred. However, if the support member is electrically conductive, the liner must be electrically insulating to electrically insulate the core member from the support member. Cavity liners are important for a number of reasons. First, they are impermeable to moisture and electrolytes. Second, they may contain flame retardants that can extinguish fires, and third, allow an easily sealable plastic material to contain the electrolyte in the hermetic seal.

During fabrication, the cavities 122 may be simultaneously filled with an electrolyte and then simultaneously formed and graded for capacity during a subsequent fabrication process. The forming process consists of charging the cell to a constant voltage, typically 4.2V, and then holding the cell at this potential for 12-48 hours. Capacity grading occurs during the charge/discharge process, where the cell is fully discharged to a low voltage, e.g. 2.5 V, then charged to the highest voltage, typically 4.2-4.5 V, then discharged again, where the capacity is Is recorded. Due to the inefficiency of the charge/discharge process, several charge/discharge cycles may be required to obtain an accurate capacity rating.

Since the cavity liner fits snugly with the core, it allows an accurate and consistent amount of electrolyte to be introduced into each core member. One way to achieve filling is to use through-holes in the sealing material 116, and then the sealing material can be filled and sealed after the electrolyte has been introduced into the cavity and treated. A jelly rolled core member having a capacity of about 3 Ah will require about 4-8 grams of electrolyte depending on the density and the surrounding porous material. Electrolyte filling is performed such that the entire jelly roll is wetted equally throughout the roll without any dry area. Each core member preferably has an equivalent amount of electrolyte between the cores with a deviation of within 0.5 g, more preferably within 0.1 g, and even more preferably within 0.05 g. The deviation is adjusted according to the total amount of electrolyte and is generally less than 5% or even more preferably <1% of the total amount of electrolyte per core. Leaving the assembly in a vacuum is helpful in this filling process and is important for complete and uniform wetting of the electrode.

The size, spacing, shape and number of the cavities 122 in the support member 120 achieves the desired operating characteristics for the battery, while at the same time achieving the safety features described above, such as mitigation of failure propagation between the core members 102. Can be adjusted and optimized to do so.

As shown in Fig. 2, the support members 220a-h may preferably have 7 to 11 different numbers of cavities, and as in the case of the support members 220d and 220h, different configurations, such as of different sizes. Can have a cavity. The number of cavities is always more than 2, and unlike the shape of the support member and the size of the jelly roll, there is no particular upper limit. The practical number of cavities is generally 2 to 30. The cavities may be uniformly distributed as in the support member 220f, or may be staggered as in the case of the support member 220g. In addition, in FIG. 2, the diameter of the cavity and the diameter of the core member that can be inserted into the cavity for each of the support members 220a-h are shown, and in addition, the capacity of each configuration is indicated in amperes (Ah).

Different types of cavities and core members can also be used. As shown in FIG. 3, the support member 320 includes a cavity 322 having an oblong shape to accommodate a core member 302 of a similar shape. In Fig. 4, the support member 420 has a mixture of an elliptical cavity 422 and a cylindrical cavity 402 to accommodate a core member (not shown) of a similar shape.

In Fig. 5, another form of a core member 502a suitable for the present invention is shown. This is a jelly roll structure having a prismatic shape other than the cylindrical or oblong shape described above. The core member includes an anode 530a, a cathode 532a, and an electrical insulating separator 534a. Although not shown in the previous figures, each core member includes a separator between the anode and the cathode. The core member 502b is prismatic, but a stacked configuration is used, and includes an anode 530b, a cathode 532b, and a separator 534b.

Until now, the core members have been shown to be electrically connected in parallel, but can be connected in series or in a combination of parallel and series connections. As shown in Fig. 6, there is a support member 620 (made of aluminum foam or polymer foam) with an inserted jelly roll core member 602. There is a tab to the core member connected to the bus bar, but for clarity, it is not shown. The negative battery terminal connector 640 is electrically connected to the low voltage bus bar 642. Positive battery terminal connector 644 is electrically connected to high voltage bus bar 646. Adjacent block bus bars 648 and 650 each connect each core member of its own row in parallel. Each bus bar 642, 644, 648 and 650 has a complementary bus bar on opposite sides of the core member, not shown. All parallel bus bars are individually connected in series via three connected bars 652, enabling a series electrical path. Sensing cables 654a-654e are located on each electrical unique point, thereby enabling detection of the voltage level across each of the parallel linked jelly roll voltage points in the series system. These wires can also be used to provide a balancing current to keep the core member in the same state of charge during charging and discharging and are connected to the feed through contact 656. One of ordinary skill in the art of battery balancing systems will appreciate the purpose of such connections in units of the invention having series connected cores.

6B shows the sealing material 616 housing the support member 320. The sealing material 616 is composed of a plastic cover 658 and a box 660 hermetically sealed through ultrasonic welding. A feed-through sensing contact 656 is positioned at an end of the sealing material 616 facing the side of the cover 658. A negative battery terminal connector 640 and a positive battery terminal connector 644 extend from the cover 658. It will be appreciated that various arrangements of the location of the connector sensing connection can be made by one of ordinary skill in the art, and that different series or parallel arrangement cells can be used for the purposes of the present invention.

In the case of a metal cover, it is closed by a welding method, such as laser welding, in the case of plastics, an adhesive (glue) is used, a thermal or ultrasonic welding method is used, or any combination can be used. This provides a properly sealed MC battery. Jelly rolls are connected in parallel or series inside the sealant.

All feedthroughs, sensing, power, pressure, etc. need to be hermetically sealed. The hermetic seal must withstand an internal pressure of at least about 1 atm and a vacuum, preferably of at least 1.2 atm. A vent set to an internal pressure lower than the seal allows may be housed in the container.

Another way to provide the balancing and sensing function is to have a separate connector that provides an external lead from each of the positive and negative terminals of the individual core member, while allowing the connector external to the container to connect with each of the individual core members. The balancing circuit will detect an imbalance in the voltage or state of charge of the series cells and provide a passive in active balancing known to those skilled in the art. The connecting lead is separate from the terminal providing a means of drawing current from the cell for the purpose of providing power from the battery, and is generally used only when the cells are connected in series within one container. The sensing leads can be selectively fused outside the container to avoid power current flowing through individual jelly rolls through the sensing circuit.

The sealing materials 116 and 616 may be composed of an egg box-shaped wall 700 of FIG. 7A so that the MC battery can be short-circuited outside the sealing material when there is a mechanical impact on the sealing material. The egg box-shaped portion 702 of the wall 700 made of aluminum contacts a plate of non-conductive material 704 made of polyethylene plastic (before impact). A second plate 706 made of aluminum or another conductive material is placed under the plastic plate 704. The egg box-shaped material 702 is connected to the negative or positive electrode of the MC battery and another conductive plate 706 is connected to the opposite pole. When there is an abnormal pressure on the wall during impact, nail penetration, or, for example, a collision, the plastic plate 704 penetrates and contacts the conductive plate 706 outside the contact points 708a-d in FIG. The egg box-shaped wall 702 is compressed to create an electrical short.

In general, the individual core members are connected by means of internal bus bars as mentioned above. Sometimes the bus bar common connector can be a wire or a plastic coated wire. It may also be a solid metal, such as copper, aluminum or nickel. This bus bar can connect a plurality of core members in series or in parallel and transmit current in the multi-core member structure to the connector to enable external connection to the multi-core array. In the case of an external bus bar, you will need a separate feed-through connector through the seal from each jelly roll.

Regardless of whether an inner bus bar or an outer bus bar is used, they can be configured to provide a fuse between the core members. This can be done in various ways, for example, by creating a region in which the cross section of the bus bar is restricted to transmit only a specific current, or by limiting the size of the tab connecting the core member to the bus bar. The bus bar or tab can be constructed from one stamped piece or other metal forming technique, or can be constructed by using a second piece that connects the division of the bus bar into a fuse arrangement. For example, if the anode and cathode tabs of 10 core members are connected by bus bars, respectively, and two square cross-sectional areas of copper bus bars with a ^{cross-sectional area of 10 mm 2 of each bus bar are used, at least one} The area can be made to have a reduced surface area compared to the rest of the bus bar. This provides a location where fusing occurs and current carrying capacity is limited. This fuse area may be between one or more points of the bus bar, preferably between each core member, but for many cells the middle point is most effective. In the event of an external short circuit, this fuse will limit the heat generation of the core member and potentially prevent thermal runaway. In addition, in the case of an internal short circuit in the core member due to a manufacturing defect or during a misuse event, for example, external penetration by a nail through the core member causing an internal short circuit in the battery, this fuse arrangement would block the failed core from other parallel cores. By doing so, you can limit the amount of current delivered to the internal short circuit.

The void space in the seal may also be filled with a shock absorbing material, such as a foam or other structure that allows for a smaller impact on the core member, further reducing the risk of internal short circuits. This ruggedization increases the resistance to shock and vibration and mechanical life by providing a means to transfer the self-vibrating frequency of the inner contents to the sealant. The filler material should preferably contain a flame retardant material capable of extinguishing any fire that may occur during the thermal runaway of the battery or be melted during the thermal runaway to absorb excess heat of the battery and limit the heat generation of the battery. This provides improved safety in case of fatal events.

Examples of flame retardants can be found in published engineering literature and handbooks, such as the Polyurethanes Handbook published in Hanser Gardner Publications, or in U.S. 5,198,473. In addition to polyurethane foam, epoxy foam or fiberglass wool and similar non-chemical or electrochemical active materials can be used as fillers in the voids inside the sealant. In particular, hollow or dense spheres or irregularly shaped particles made of plastic, metal or ceramic can be used as low-cost fillers, and in the case of hollow spheres, they will provide additional means for energy absorption during collision scenarios in multi-core cells. . In special cases, the supporting member is aluminum foam. In another special case, the support member is a dense aluminum foam with 10-25% of the aluminum density. In another special case, the pores in the aluminum foam have an average diameter of less than 1 mm.

When the MC battery has only core members arranged in parallel, the core member may include one or more core members optimized for power and one or more core members optimized for energy. In another special case, the MC battery may have an anode using a specific material or another core member using a cathode and an anode using a different material than the core member with the cathode. In another special case, the anode or cathode may have electrodes of different thickness. Any combination with various electrode thicknesses, cathode or anode active materials, or electrode formulations can be combined into parallel strings for the purpose of matching the energy to power ratio of the battery. Some core members may be configured to withstand fast power pulses, while others are optimized for high energy storage to provide a battery capable of handling high power pulses while having a high energy content. However, it is important that the core member has an electrochemically matched chemistry to provide chemical stability in the voltage window for the selected chemistry.

For example, as long as an upper potential of 4.2 V is used and a lower potential of about 2 V to 2.5 V is used, the LiCoO ₂ cathode is LiNi _{0 . 8} Co _{0 . 15} Al _{0 . 05} O ₂ Can be matched with cathode, but when the potential exceeds about 4.2 V, e.g., when it becomes 4.3 V, magnesium doped LiCoO ₂ The material should not match the NCA material, because the NCA material degrades at higher voltages. However, in the latter case, the two materials can be mixed as long as the upper potential is limited to 4.2V. It is an object of the present invention to use a cathode material blended in the correct voltage range, and the inventors have found a particular combination that is particularly useful for high energy or high power, detailed in the following description.

Power and energy optimization can be achieved by adjusting the formulation of the electrode, such as by using a higher degree of conductive additive for increased electrical conductivity, or by using electrodes of different thickness. Also, the energy core can have one set of active materials (cathode and anode) and the power core can have another type of material. When using this method, it is desirable that the material has a matched voltage range, e.g. 2.5-4.2V or 2.5V-4.5V for high voltage combinations, to prevent degradation. The upper voltage per insulating core member in a Li-ion multi-core battery is characterized as greater than 4.2V, typically less than 5V.

The following is a description of an anode, a cathode, a separator, and an electrolyte that can be used in connection with the present invention.

Anode

The anodes of these core members are commonly found in Li-ion or Li polymer batteries and are described in the literature, such as graphite, doped carbon, hard carbon, amorphous carbon, silicon (e.g., silicon nanoparticles or carbon containing Si pillars or dispersed), tin, tin alloy, Cu ₆ Sn ₅ , Li, Li deposited on a metal foil substrate, Si containing Li, Li metal powder mixture in graphite, lithium titanate and mixtures thereof. . Anode suppliers include, for example, Morgan Carbon, Hitachi Chemical, Nippon Carbon, BTR Energy, JFE Chemical, Shanshan, Taiwan Steel, Osaka Gas, Conoco, FMC Lithium, and Mitsubishi Chemical. The invention is not limited to any particular anode compound.

Cathode

The cathode used for the jelly roll is an industry standard and a new high voltage mixture that is described in detail below. These new cathodes can be used in MC structures or single cell batteries and the anode/cathode structures are enclosed in enclosed metal canisters or enclosed polymer bags. Due to the abundance of cathode materials that can be used in the industry, the type of material for each group of materials is referred to herein as a “compound,” where each compound can have a variety of composition and can be used in crystal structure, chemical composition, voltage range compatibility, or They are grouped due to the similarity of material composition and gradient changes. Examples of suitable individual materials are Li _x CoO ₂ (referred to as compound A), Li _x M _z Co _w O ₂ (compound B, where M is selected from Mg, Ti and Al and partially contains Co or Li in the crystal lattice. Substituted and added with Z=0-5%, in general W is close to 1, suitable for charging exceeding 4.2V), Li _x Ni _a Mn _b Co _c O ₂ (especially about a=1/3, b=1/3, c=1/3 (compound C) and a=0.5, b=0.3, c=0.2 (compound D), and Mg substituted compounds thereof (both grouped by compound E).

Another example is Li _x Ni _d Co _e Al _f O ₂ (Compound F) and its Mg substituted derivative Li _x Mg _y Ni _d Co _e Al _f O ₂ (Compound G), in special cases, d=0.8 , e=0.15, f=0.05, but d, e and f can vary by a few percent, and y is from 0 to 0.05. Other examples of individual cathode materials are Li _x FePO ₄ (Compound H), Li _x CoPO ₄ (Compound I), Li _x MnPO ₄ (Compound J) and Li _x Mn ₂ O ₄ (Compound K). In compounds, an excess of lithium is generally found (x>1), but X can be between about 0.9 and 1.1. Types of materials that are particularly suitable for high voltages, which have a high capacity when charged above 4.2 V, are described for example in Thackeray et al. US Pat. No. US7,358,009 and there are commercially available so-called rare-layered materials from BASF and TODA. (Compound L).

The compounds first described in Thackeray can be stable at voltages in excess of 4.2V. Some of these cathodes are stable at high voltages in excess of 4.2V (standard peak voltage using graphite as the anode) and preferably these materials can be mixed. Although any of the above substances can be used in the present invention, it is preferred to mix two or more substance compounds selected from B, C, D, E, F, G, I, J and L. In particular, mixtures of two or more components of compounds B, D, F, G and L are preferred. For very high energy density configurations, a mixture of (B and L) or (B and G) or (G and L) is most beneficial, and high power can also be achieved when they are made of thin electrodes. Thin (power) and thick (energy) electrodes can fit within the core member to tailor the energy to power ratio while having the same suitable voltage range and chemistry.

Certain new cathodes, so-called Core Shell Gradient (CSG) materials (referred to as Compound M), have different core compositions compared to their own shells. For example, Ecopro (website www.ecopro.co.kr or (http://ecopro.co.kr/xe/?mid=emenu31, 2010-10-01) or patent application and registration number PCT/KR2007 /001729 (PCT) (2007) in the product literature as compound M substances, such as "CSG substances" as _{xLi [Ni 0.8} Co _0.1 Mn _0.1 ]O ₂ (1-x)Li[ Ni _0.46 Co _0.23 Mn _0.31 ]O ₂ (Core Shell Gradient) is described, another M-type compound is described in YK Sun's ElectrochimicaActa Vol.55 Issue 28 p.8621-8627, and the third description of the M-type compound is Nature Materials 8 (2009 ) can be found in p.320-324 (non-paper YK Sun), where similar composition but Formula bulk _{= Li (Ni 0. 8 Co} 0. 1 Mn 0. 1 O 2, the concentration gradient = Li (Ni _{0.8 -x} Co _0.1+y Mn _0.1+z , where 0≤x≤0.34, 0≤y≤0.13, and 0≤z≤0.21, and the surface layer = Li(Ni _0.46 Co _0.23 Mn _0.31 )O ₂ CSG material A fourth description can be found in WO2012/011785A2 ("785A2" patent), where Li _x1 [Ni _1-y1-z1-w1 Co _y1 Mn _z1 M _w1 ]O ₂ (wherein , 0.9≤x1≤1.3, 0.1≤y1≤0.3, 0.0≤z1≤0.3, 0≤w1≤0.1 and M is Mg, Zn, Ca, Sr, Cu, Zr, P, Fe, Al, Ga, In, Cr , Ge, and at least one metal selected from Sn), and the outer part is Li _x2 [Ni _1-y2-z2-w2 Co _y2 Mn _z2 M _W2 ]O ₂ (In this case, in the external formula, 0.9≦x2≦1+ z2, 0≤y2≤0.33, 0≤z2≤0.5, 0≤w2≤0.1 and M is Mg, Zn, Ca, Sr, Cu, Zr, P, F e, being at least one metal selected from Al, Ga, In, Cr, Ge, and Sn). All four ranges of modifications of compound M are incorporated herein by reference for compound M used in the various aspects of the invention.

The M compound may be about 1, but may additionally have a Li content that may vary within a few percent, and the Li or Ni/Mn/Co compounds may be substituted with Mg, Al and first row transition metals by optimization, these It is preferred that at least one of the M compounds is blended as previously described with compounds B, C, D, E, F, G, L for use in Li-ion batteries. The core compound M material may contain up to 90% nickel and 5% cobalt and up to 40% Mn, and the gradient will be 10% Ni, 90% cobalt, and 50% Mn in one of these boundary compositions. .

In general, high power can be achieved by using thin electrodes of the compounds or blends described herein for the anode and cathode. Thick electrodes are generally considered to be from more than 60 μm to about 200 μm when measuring the electrode coating layer thickness in aluminum foil, while thinner electrodes (i.e., less than 60 μm) are better for high power Li-ion battery configurations. In general, in the case of high power, more carbon black additives can be used in electrode formulations to increase electrical conductivity. Cathode compounds are available from several material suppliers, such as Umicore, BASF, TODA Kogyo, Ecopro, Nichia, MGL, Shanshan and Mitsubishi Chemical. Compound M is available from Ecopro and CSG material in its product literature (e. _{G., XLi [Ni 0.8 Co 0.1 Mn} 0.1] O 2 (1-x) Li [Ni 0. 46 Co 0. 23 Mn 0. 31] O 2 ] And another M-type mixture is also described in YK Sun in ElectrochimicaActa, Vol. 55, Issue 28, p.8621-8627, all of which may be preferred to be blended with a compound as previously described. .

It may be desirable to coat the high voltage cathode with compound AM blended as two or more compounds with a surface modifier. When a surface modifier is used, it is not necessary, but preferred, that each compound is coated with the same surface modifier. The surface modifier helps to increase the first cycle efficiency and speed performance of the cathode mixture. In addition, the useful life is improved by applying the surface modifying material. Examples of surface modifiers are Al ₂ O ₃ , Nb ₂ O ₅ , ZrO ₂ , ZnO, MgO, TiO ₂ , metal fluorides such as AlF ₃ , metal phosphates AlPO ₄ and CoPO ₄ . Such surface-modifying compounds have been previously described in J. Liu et al., J. of Materials Chemistry 20 (2010) 3961-3967; ST Myung et al., Chemistry of Materials 17 (2005) 3695-3704; STMyung et al. J. of Physical Chemistry C 111 (2007) 4061-4067; ST Myung et al. J. of Physical Chemistry C 1154 (2010) 4710-4718; BC Park et al., J. of Power Sources 178 (2008) 826-83; J.Cho et al., J of Electrochemical Society 151 (2004) A1707-A1711], but no reports have been made regarding cathodes blended at voltages exceeding 4.2V. It is particularly advantageous to blend the surface modified compounds B, C, D, E, F, G, L and M for operation above 4.2V.

The anode material is mixed with a binder and carbon black, such as ketjen black or other conductive additives. NMP is generally used to dissolve the binder and PVDF is the preferred binder for Li-ions, and Li polymer types may have other binders. Cathode slurries are mixed to a stable viscosity and are well known in the art. The previously described compounds A-M and blends thereof are often collectively referred to herein as “cathode active material”. Similarly, the anode compound is referred to as an anode active material.

Cathode electrodes can be prepared, for example, by mixing a cathode compound, such as a blend of compounds A-M above or individual compounds, in about 94% cathode active material and about 2% carbon black and 3% PVDF binder. Carbon black can be Ketjen black, Super P, acetylene black and other conductive additives available from various suppliers, such as AkzoNobel, Timcal, and Cabot. Mixing these components with an NMP solvent produces a slurry, which is then coated on both sides of an aluminum foil about 20 micrometers thick and dried to about 100-130[deg.] C. at the desired thickness and area weight. This electrode is calendered by a roll to the desired thickness and density.

Anodes are prepared similarly, but for graphite, about 94-96% anode active material is commonly used, whereas PVDF binder is 4%. Sometimes SBR binders are used for the cathode mixed with CMC and for this type of binder a relative amount of anode active material of about 98% can generally be used. In the case of the anode, carbon black can sometimes be used to increase speed performance. The anode is coated on about 10 micrometers of copper foil.

Those skilled in the art can easily mix the composition as previously described for the functional electrode.

Fiber materials of PE, PP and carbon may optionally be added to the electrode formulation to limit electrode expansion during charging and discharging. Another expansion technique uses inert ceramic particles such as SiO ₂ , TiO ₂ , ZrO ₂ or Al ₂ O ₃ in the electrode formulation. In general, the density of the cathode is 3 to 4 g/cm ³ , preferably 3.6 to 3.8 g/cm ^3, and the graphite anode is 1.4 to 1.9 g/cm ³ , preferably 1.6 to 1.8 g/cm ³ , which is Is achieved by

Separator

The separator has a form of an electrically insulating film interposed between the anode electrode and the cathode electrode, and needs to have high permeability to Li ions and high tensile strength and high penetration strength in the traveling direction. The pore size is generally 0.01 to 1 micrometer and the thickness is 5 micrometers to 50 micrometers. Sheets of nonwoven polyolefins, such as polyethylene (PE), polypropylene (PP) or PP/PE/PP structures, are generally used. In general, _{a ceramic composed of Al 2} O ₃ is applied onto a film to improve shrinkage during heating and improve protection against internal short circuits. Likewise the cathode or anode can be coated with ceramics. Separators can be sourced from several suppliers in the field, such as Celgard, SK, Ube, Asahi Kasei, Tonen/Exxon and WScope.

Electrolyte

Electrolytes are generally known in the art to contain a solvent and a salt. Solvents are generally DEC (diethyl carbonate), EC (ethylene carbonate), EMC (ethyl methyl carbonate), PC (propylene carbonate), DMC (dimethyl carbonate), 1,3 dioxolane, EA (ethyl acetate), tetrahydro It is selected from furan (THF). The salt is selected from LiPF ₆ , LiClO ₄ , LiAsF ₆ , LiBF ₄ , sulfur, or an imide-containing compound used in the electrolyte, such as LiCFSO ₃ , LiN(CF ₃ SO ₂ ) ₂ , LiN(CF ₃ CF ₂ SO ₂ ) ₂ Or by bubbling _{SO 2} through a premixed electrolyte such as EC/EMC/DMC (1:1:1 ratio) and 1M LiPF _6. Other salts are LiBOB (lithium bis-oxalateborate), TEATFB (tetraethylammonium tetrafluoroborate), and TEMABF ₄ (triethylmethylammonium tetrafluoroborate). Additives for effective SEI formation, gas generation, flame retardant properties, or redox carrying capacity can also be used, e.g. BP (biphenyl), FEC, pyridine, triethylphosphite, triethanolamine, ethylenediamine, hexa Phosphorictriamide, sulfur, PS (propylene sulfite), ES (ethylene sulfite), TPP (triphenyl phosphate), ammonium salts, halogen-containing solvents such as carbon tetrathride or ethylene trifluoride and further CO2 gas can be used to improve high temperature storage properties. For solid/gel or polymer electrolytes, PVDF, PVDF-HFP, EMITFSI, LiTFSI, PEO, PAN, PMMA, PVC, any blend of these polymers can be used with other electrolyte components to provide a gel electrolyte. Electrolyte suppliers include Cheil, Ube, Mitsubishi Chemical, BASF, Tomiyama, Guotsa-Huasong, and Novolyte.

There are electrolytes that work in both supercapacitors (with electrochemical double layers) and standard Li-ion batteries. For these electrolytes, one or more supercapacitor cores can be mixed with one or more common Li-ion core members in the sealant, so that the supercapacitor component functions as a power agent and the Li-ion core member is an energy harvesting agent. Functions as

example

In this example, a set of five cylindrical jelly roll type core members are connected in parallel to two common bus bars (positive and negative), which is the MC battery shown in Fig. 1, except that it has only half of the core members. It is similar to the composition. A negative connector is connected to a tab extending from the anode foil (copper) of the jelly roll, has a coated graphite electrode, and the positive connector to the cathode foil (aluminum) of the jelly roll is a blended oxide electrode of compound M and compound F. Has a structure. The anode tab made of nickel and the cathode tab made of aluminum are welded to the bus bar using spot welding or laser welding techniques. The sealing material and the supporting member are made of plastic material (polyethylene). In this example, a cylindrical cavity with 18 mm diameter and a jelly roll core member with a slightly smaller diameter (17.9 mm) was used. The sealant and cover are ultrasonically welded together to make a plastic material that creates an airtight seal.

Those skilled in the art of the sale can select and modify the properties of the core member as described above, and achieve a high energy or high power core. The table shown below summarizes three examples in which the core composition of the five core member examples described above are different, and the properties of the MC battery that can be achieved are different.

The present invention can be implemented in other specific forms within its spirit and essential characteristics. Accordingly, this embodiment should be regarded as illustrative and not restrictive in all respects.

Claims (32)

As a multi-core lithium-ion battery,
A support member comprising a plurality of cavities formed by a cavity surface, each cavity of the plurality of cavities configured to receive a lithium ion core member through a cavity opening,
A plurality of lithium ion core members, wherein each lithium ion core member of the plurality of lithium ion core members includes an anode, a cathode, a separator positioned between the anode and the cathode, and an electrolyte-, And
Hermetically sealed sealing material surrounding and sealing the support member
Including, wherein each lithium ion core member of the plurality of lithium ion core members is located in one of the plurality of cavities of the support member,
Each of the lithium ion core members is surrounded by the cavity surface of one of the plurality of cavities along its length, so that it cannot escape from the cavity containing the electrolyte,
The hermetically sealed sealing material is a shared atmosphere in which (i) each of the cavities is open, and (ii) the anode, cathode, and electrolyte of each ion core member are directly exposed through the cavity opening when positioned within the cavity of the support member. Define the area,
At least one of the support member and the sealing material is made at least partially from an insulating mineral material. The lithium ion battery according to claim 1, wherein the support member comprises a kinetic energy absorbing material. The lithium ion battery of claim 2, wherein the kinetic energy absorbing material is formed of one of aluminum foam, ceramic and plastic. The lithium ion battery of claim 1, further comprising a cavity liner positioned within each cavity, each cavity liner being formed of a plastic or aluminum material and receiving one of the lithium ion core members. 5. The lithium ion battery of claim 4, wherein the plurality of cavity liners are formed as part of a monolithic liner member. The lithium ion battery according to claim 1, further comprising an electrical connector in the hermetically sealed sealant for electrically connecting the ion core member to an electrical terminal outside the hermetically sealed sealant. The method of claim 6, wherein the electrical connector comprises a first bus bar and a second bus bar, and the first bus bar interconnects an anode of the ion core member to both terminal members of a terminal outside the hermetically sealed sealant, And the second bus bar interconnecting the cathode of the ion core member to the negative terminal member of the terminal outside the hermetically sealed sealant. The lithium ion battery according to claim 1, wherein the support member has a shape of a honeycomb structure. 3. The lithium ion battery of claim 2, wherein the kinetic energy absorbing material comprises a compressible medium. The lithium ion battery of claim 1, wherein the hermetically sealed seal comprises a wall having a compressible element that creates an electrical short of the lithium ion battery when compressed due to a force impinging on the wall. The lithium ion battery according to claim 1, wherein the plurality of cavities included in the support member and their corresponding ion core members have a shape of one of a cylindrical shape, an oblong shape, and a prism. 12. The lithium ion battery according to claim 11, wherein at least one of the plurality of cavities and a corresponding ion core member thereof have a different shape than the rest of the plurality of cavities and a corresponding ion core member thereof. The lithium ion battery according to claim 1, wherein at least one of the ion core members has high power characteristics and at least one of the ion core members has high energy characteristics. The method of claim 7, further comprising a tab for electrically connecting each anode to the first bus bar and a tab for electrically connecting each cathode to the second bus bar, each tap exceeding a specified current A lithium ion battery comprising means for stopping the flow of electrical current through each of the tabs when applied. The method of claim 7, wherein the first bus bar includes a fuse element close to each interconnection point between the anodes of the first bus bar, and the second bus bar is between the cathodes of the second bus bar. A lithium ion battery comprising a fuse element proximate each interconnection point to stop the flow of electrical current through the fuse element when a specified current is exceeded. The lithium ion battery according to claim 1, wherein the hermetically sealed sealing material comprises a flame retardant member. The lithium ion battery according to claim 1, wherein the hermetically sealed sealing material forms a lithium ion battery area and the shared atmosphere area inside the hermetically sealed sealing material. The lithium ion battery according to claim 1, further comprising a protective sleeve surrounding each of the ion core members. The lithium ion battery according to claim 1, wherein the support member is electrolyte absorbent. The lithium ion battery according to claim 1, wherein the support member is deformable in response to an impact load and absorbs kinetic energy. 5. The lithium ion battery of claim 4, wherein the cavity liner is moisture and electrolyte impermeable. The lithium ion battery according to claim 1, wherein the cavity is unevenly distributed within the support member. The lithium ion battery according to claim 1, wherein the cavities are staggered in the support member. The lithium ion battery according to claim 16, wherein the flame retardant member comprises a flame retardant mesh material attached to the outside of the hermetically sealed sealant. The lithium ion battery according to claim 16, wherein the flame retardant member is selected from the group consisting of polyurethane foam, epoxy foam, and glass fiber wool. The lithium ion battery according to claim 16, wherein the flame retardant member comprises a filler material located in an empty space inside the hermetically sealed sealant. The lithium ion battery according to claim 26, wherein the filler material is selected from the group consisting of hollow spheres, dense spheres, and irregularly shaped particles, and the filler material is made of a plastic, metal or ceramic material. The lithium ion battery according to claim 1, wherein each of the ion core members is introduced into the cavity of the support member without a separate hermetic sealant. 5. The lithium ion battery of claim 4, wherein each cavity liner is moisture and electrolyte impermeable. The lithium ion battery of claim 1, wherein the insulating mineral material is selected from the group consisting of alkaline earth silicate wool, basalt fiber, asbestos, volcanic glass fiber, fiberglass, cellular glass, and any combination thereof. The lithium ion battery of claim 1, wherein the insulating mineral material further comprises a binding material selected from the group consisting of nylon, PVC, PVA, acrylic polymer, and any combination thereof. The lithium ion battery of claim 1, wherein the insulating mineral material further comprises a flame retardant additive.

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