A technique for an access node to synchronize the accessibility of a plurality of access nodes within a network is described. The technique receives an accessibility update and/or device update from a remote node. For the accessibility update, the access node compares entries in the accessibility update to the local accessibility table. If entries in the accessibility update are more up-to-date than the local accessibility table, the access node adjusts the local accessibility table to reflect the updates. The local access node compares the node identifier, heartbeat, and timestamp to determine whether and entry in the local accessibility table is up-to-date. For the device update, the access node compares entries in the device update to the local device table. If entries in the device update are more up-to-date than the local device table, the access node adjusts the local device table to reflect the updates.

In a data and/or communication network, clients (e.g., devices) may write object values or read current object values in a database to adjust the state of one or more devices (e.g., dim light, set temperature, etc.). For concurrent processes (e.g., writes and reads), a single centralized database at an access node typically ensures that any client (e.g., device) does not read a value from an object that is older (e.g., stale values) than a value that one or more clients (e.g., devices) have already successfully written to the centralized database. Even though this strict consistency of the centralized database ensures data integrity, the centralized access node has scalability restraints. A client's (e.g., device's) physical proximity from the access node, for example, becomes an issue where clients (e.g., devices) that are physically located farther away from central access node have a higher latency than clients (e.g., devices) physically located closer to the central access node. In addition, the clients (e.g., devices) of a centralized database infrastructure rely on the access node to function properly. That is, not only does each client (e.g., device) lose connectivity if/when an access node goes offline (e.g., fail), but some of the clients (e.g., devices) lose proper functionality, as the clients (e.g., devices) cannot read an object or write an object from the centralized database until the access node is brought back online.
One approach to maintain the connectivity and/or functionality of clients (e.g., devices) is to decentralize the database and replicate the database across additional access nodes. This approach has the potential to compensate for offline access nodes and for some clients (e.g., devices) the approach may decrease latency between clients (e.g., devices).
Efforts, however, to ensure that the data is eventually consistent across each access node such that the object values will eventually contain the same value between replicas absent any new writes to an object value to any node, fall short. This shortfall is particularly poignant for access nodes that support internet-of-thing (IoT) devices, which may have multiple communication protocols such as Bluetooth, Zigbee, Z-wave, 6lowPAN, Thread, WiFi, cellular, Nearfield Communication (NFC), Sigfox, Neul, LoRaWAN, to name a few.

Distributed database for synchronizing the accessibility of nodes and shared devices


A flexible pouch for medical implements is manufactured from a disposable material which can be easily sterilized and includes a plurality of pockets for holding forceps, scissors, and similar surgical tools. The pouch includes plastic loops for holding cords or medical tubing and a bendable aluminum strap designed to retain a rolled towel. Additionally, one or more sections of the pouch can be formed from several layers of material with a thin magnet positioned between the layers for the purpose of holding the tools firmly secured thereto after they have been removed from their individual pockets. Peel-off adhesive strips are disposed around one or more edges of the pouch to facilitate a secure engagement thereof with a supporting surface.

1. Field of the Invention
The present invention relates to flexible tool kits, and more particularly pertains to a flexible implement holding pouch which may be used for holding implements associated with the medical profession.
2. Description of the Prior Art
The use of flexible tool holding pouches is known in the prior art. More specifically, flexible tool pouches heretofore devised and utilized for the purpose of storing and retaining tools during periods of non-use are known to consist basically of familiar, expected and obvious structural configurations, notwithstanding the myriad of designs encompassed by the crowded prior art which have been developed for the fulfillment of countless objectives and requirements.
More particularly, the flexible tool pouches is presently available in the art are substantially limited in both concept and function inasmuch as they are designed primarily as a tool storage means. The pouches are often constructed of materials which are rugged and cumbersome inasmuch as such materials add to the durability of the pouches per se, and little or no thought has been given to the idea of utilizing the pouches in an operable environment, e.g., such as during a medical operation. Such specialized pouches, if they were available, would have to be constructed from materials which could be easily sterilized and possibly, though not necessarily, reused. Further, provisions would have to be made for securing both the pouches and their associated tools in a fixed and stable position during a usage thereof. Apparently, such pouches are not presently available in the commercial market.
Therefore, it can be appreciated that there exists a continuing need for new and improved flexible tool pouches which can be used in specialized professions such as the medical field or the like. In this regard, the present invention substantially fulfills this need.

Flexible medical implement utility pouch


A semiconductor light emitting device includes a lead frame 1 covered by a resin package 2. The lead frame 1 includes first and second leads 1A and 1B facing each other. The first and second leads 1A and 1B include inner lead sections 11 and 12 covered with the package 2, respectively. The first and second leads 1A and 1B include outer lead sections 13 protruding from package 2 ends. First and second exposed surfaces 51 and 52 are exposed from the package 2 in the first and second lead lower surfaces, respectively. The first lead 1A is longer than the second lead 1B. An LED 3 is mounted on the first lead upper surface. The second lead 1B includes second end portions 15 extending in the second exposed surface 52 from the both ends of the facing surface toward the first lead 1A.

1. Field of the Invention
The present invention relates to a semiconductor light emitting device that includes a semiconductor light emitting element such as a light emitting diode, and a method for producing the semiconductor light emitting device.
2. Description of the Related Art
In recent years, semiconductor light emitting devices such as the light emitting diodes (hereinafter also referred to as LEDs), which have low power consumption, are becoming more popular instead of conventional filament lamps in general lighting lamp applications. The applications of semiconductor light emitting devices broaden to light sources for vehicles from lights sources for lighting.
FIGS. 11 and 12 show an example of the semiconductor light emitting device (see WO2012/014,382 A1). This semiconductor light emitting device includes a lead frame 81; a semiconductor element 83 held by the lead frame 81; a frame body 82 formed on the lead frame 81 to surround the semiconductor element 83, cover a side surface of the lead frame 81, and expose a bottom surface of the lead frame 81; and a protective resin (not shown) filling a region surrounded by the frame body. The lead frame 81 includes a die pad section 81A, and a lead section 81B. The die pad section 81A, and the lead section 81B are arranged away from each other and fixed to the lead body 82 so that they are electrically isolated from each other. The die pad section 81A is longer than the lead 81B. The semiconductor element 83 is mounted on the upper surface of the die pad portion 81A having a larger area.
After resin is formed as the frame bodies 82 on the lead frames 81, as shown in FIG. 13, the lead frames 81 are cut from each other along the single-dot-dashed lines in FIG. 13 so that the semiconductor light emitting devices are manufactured. However, in the process for manufacturing the semiconductor light emitting devices, as shown in a bottom view of FIG. 14, a crack 85 may be produced in the peripheral edge part on the lead 81B side, or the like by a shock when cutting the lead frames 81 from each other (see the arrows A in FIG. 12). This crack 85 may cause quality deficiencies, which may lead to reduce the reliability of the semiconductor light emitting element.
See also Laid-Open Patent Publication No. JP 2012-209,377 A.
It is one object of the present invention to provide a semiconductor light emitting device including a resin package that can be effectively prevented from being damaged by a shock when an external force is applied to a lead frame whereby improving its reliability, and a method for producing the semiconductor light emitting device.

Semiconductor light emitting device and method for producing the same


The present invention restrains adverse effects caused by refraction of a terahertz wave by a device under test when the terahertz wave is fed to the device under test for measurement. A container 10 contains at least part of a device under test 1 to be measured by a terahertz wave measurement device. The container 10 includes a gap portion 11 that internally arranges at least a part of the device under test 1, and an enclosure portion 12 that includes a first curved surface portion S1, and a second curved surface portion S2, and arranges the gap portion 11 between the first curved surface portion S1 and the second curved surface portion S2, thereby enclosing the gap portion 11. Moreover, a relationship n1<n2 holds where n2 is the refractive index of the enclosure portion, and n1 is the refractive index of the device under test. Further, both the first curved surface portion S1 and the second curved surface portion S2 are convex surfaces.

1. Field of the Invention
The present invention relates to tomography using an electromagnetic wave (frequency thereof is equal to or more than 0.01 [THz], and equal to or less than 100 [THz]) (such as a terahertz wave (frequency thereof is equal to or more than 0.03 [THz], and equal to or less than 10 [THz]), for example).
2. Description of the Prior Art
There has conventionally been the computed tomography (CT) as a method for obtaining tomographic information on a device under test. This method carried out while a generator and a detector of the X ray are used is referred to as X-ray CT. With the X-ray CT, it is possible to acquire tomographic information on a human body in non-destructive and non-contact manner.

Container, a method for disposing the same, and a measurement method


A video communication apparatus for encoding a video signal representative of a scene being picked up by a video camera and transmitting the encoded signal. The apparatus generates, in response to a synchronizing signal synchronous to the video signal, signals representative of a predetermined pick-up area to be encoded which is smaller than the entire pick-up area being picked up by the video camera, and a signal representative of a position of the predetermined pick-up area in the entire pick-up area. These signals mark the predetermined pick-up area with the entire pick-up area. A memory stores video data associated with either one of the entire pick-up area and the predetermined pick-up area.

1. Field of the Invention
The present invention relates to a television (TV) conference system, TV telephone or similar video communication apparatus.
2. Description of the Prior Art
In the video communication apparatuses art to which the present invention pertains, it is often required that every participant attending a TV conference be picked up in an adequate image size and at an adequate position on the screen of a display device. An implementation elaborated to meet this requirement in relation to TV conferences is disclosed in Japanese Laid-Open Patent Publication (Kokai) No. 208184/1985.
The implementation disclosed in the above-mentioned Laid-Open Patent Publication uses two exclusive cameras, i.e., one for extracting contours only and the other for shooting individual participants in a conference. An electrically driven zoom lens and a motor French mount are mounted on the second-mentioned camera. The first-mentioned camera for extracting contours picks up the background of a conference room without participants, and the entire scene in which participants are seated. The background image and the entire image inclusive of the participants are switched over by a switch and stored in independent memories. A differential circuit produces a differential between the background image and the entire image or participant image to thereby remove the background. The resulting video signal representative of the participants only is fed to a contour extracting circuit, whereby the contours of individual participants are extracted. A vertical correlation circuit receives a contour signal from the contour extracting circuit and in turn produces a seat signal which shows the positions where the participants are seated. In response to the seat signal, the zooming of the zoom lens and the pan and tilt of the motor French mount which are mounted on the entire scene pick-up camera are adjusted, thereby shooting each of the participants in an adequate size and an adequate position.
A drawback of the prior art apparatus discussed above is that the motor French mount and other mechanically movable parts are essential to the adjustment of the area to be picked up, resulting in a bulky and expensive construction. Even with a TV telephone, the camera has to be adjusted in pointing mechanically by hand to match it to the person's sitting height or the position of a chair, or the TV telephone itself has to be provided with an oscillatable structure. Hence, it is impracticable to fix the camera in place within a hermetic casing or to fix the TV telephone itself in a desired position.

Video communication apparatus capable of electronically adjusting the field of view of a video frame


An integrated circuit package which utilizes a standard TAB tape that can couple a lead frame to one of a number of integrated circuit dies that have different outer dimensions. The TAB tape includes a sheet of polyimide which supports a plurality of conductive leads. The sheet has a rectangular center opening which provides clearance for the IC die. Adjacent to each edge of the center opening are a plurality of equally spaced contact openings which expose portions of the leads. The leads are coupled to the integrated circuit by attaching the contact portions to the surface pads of the die. The contact openings are located at various distances from the center opening so that the tape can accommodate different die sizes. The leads of the TAB tape are also attached to a lead frame through lead frame openings in the polyimide.

1. Field of the Invention
The present invention relates to an integrated circuit package.
2. Description of Related Art
Most commercially available integrated circuits (ICs) are housed within a plastic or ceramic package. The IC is typically coupled to a lead frame which has leads that extend from the exterior of the package. The leads are soldered to a printed circuit board which couples the IC to other electrical devices.
The lead frames are typically coupled to the integrated circuit die by using either a number of individual wires (wire bonding) or a tape which has a plurality of leads (TAB tape). Each TAB tape contains a sheet of dielectric which has a plurality of conductive leads etched into a pattern along one surface of the tape. The TAB tape is typically rectangular in shape and includes a center opening which provides clearance for the IC die. The leads each have a finger portion which extends beyond the center opening of the tape and are bonded to contact bumps located on the outer edge of the die.
To reduce the cost of producing integrated circuit packages, it is desirable to construct a single package which can house a variety of die sizes. Installing various size dies using conventional TAB tape requires that each tape be constructed so that the leads are long enough to attach the lead frame to the contact bumps of the die. This typically requires varying the size of the center opening so that the leads of the tape match the profile of the die. Each die size therefore has a corresponding TAB tape. Using a number of different TAP tape sizes, increases the complexity of assembling the package. It would therefore be desirable to have a single TAB tape which can couple a lead frame to any one of a number of different IC dies.

Method and apparatus of coupling a die to a lead frame with a tape automated bonded tape that has openings which expose portions of the tape leads


A lens driving device including: a fixing part disposed in such a manner that the fixing part is separated from the movable part in the direction of the optical axis; and suspension wires that extend along the direction of the optical axis and support the movable part with respect to the fixing part in such a manner that the movable part is displaceable in the direction orthogonal to the direction of the optical axis, a first end of each suspension wire being fixed to the fixing part, a second end of each suspension wire being fixed to the movable part, in which the fixing part includes a base member and a wire connecting member, the wire connecting member including a main body part and a wire connecting part exposed from the base member, the first end of each suspension wire being fixed to the wire connecting part.

Conventionally, various lens holder drive apparatuses for capturing a clear image by preventing blurring on the imaging surface even with hand shake (vibration) when capturing an image of a still picture have been proposed.
For example, PTL 1 discloses a hand shake correction device in which a permanent magnet for an auto-focus (AF) lens driving device serves also as a permanent magnet for a hand shake correction device for the purpose of achieving reduction in size and height.
In the hand shake correction device disclosed in PTL 1, the OIS fixing part is separated from the OIS movable part in the light axis direction on the rear side of the OIS movable part serving also as the auto-focusing lens driving device. One ends of (lower ends) a plurality of suspension wires are fixed at the outer periphery part of the OIS fixing part. The other ends (upper ends) of the suspension wires are firmly fixed to the OIS movable part.
To be more specific, in the hand shake correction device disclosed in PTL 1, the one ends (lower ends) of the suspension wires are fixed at the four corners of the coil substrate for holding the OIS coil in the OIS fixing part. The coil substrate is disposed on the OIS movable part side relative to the base member in the OIS fixing part. It is to be noted that the base member is aimed at positioning of the coil substrate and the sensor substrate in the OIS fixing part.

Lens driving device, camera module, and camera mounting apparatus


A computer-implemented method for forming a dataset configured for learning a neural network. The neural network is configured for inference, from a freehand drawing representing a 3D shape, of a solid CAD feature representing the 3D shape. The method includes generating one or more solid CAD feature includes each representing a respective 3D shape. The method also includes, for each solid CAD feature, determining one or more respective freehand drawings each representing the respective 3D shape, and inserting in the dataset, one or more training samples. Each training sample includes the solid CAD feature and a respective freehand drawing. The method forms an improved solution for inference, from a freehand drawing representing a 3D shape, of a 3D modeled object representing the 3D shape.

A number of systems and programs are offered on the market for the design, the engineering and the manufacturing of objects. CAD is an acronym for Computer-Aided Design, e.g. it relates to software solutions for designing an object.
CAE is an acronym for Computer-Aided Engineering, e.g. it relates to software solutions for simulating the physical behavior of a future product. CAM is an acronym for Computer-Aided Manufacturing, e.g. it relates to software solutions for defining manufacturing processes and operations. In such computer-aided design systems, the graphical user interface plays an important role as regards the efficiency of the technique. These techniques may be embedded within Product Lifecycle Management (PLM) systems. PLM refers to a business strategy that helps companies to share product data, apply common processes, and leverage corporate knowledge for the development of products from conception to the end of their life, across the concept of extended enterprise. The PLM solutions provided by.
Dassault Systemes (under the trademarks CATIA, ENOVIA and DELMIA) provide an Engineering Hub, which organizes product engineering knowledge, a Manufacturing Hub, which manages manufacturing engineering knowledge, and an Enterprise Hub which enables enterprise integrations and connections into both the Engineering and Manufacturing Hubs. All together the system delivers an open object model linking products, processes, resources to enable dynamic, knowledge-based product creation and decision support that drives optimized product definition, manufacturing preparation, production and service.
In this context, researchers have been looking for solutions to infer a 3D modeled object representing a 3D shape from a freehand drawing representing the 3D shape. The following references notably relate to this issue:                [1] T. Igarashi, S. Matsuoka, and H. Tanaka, "Teddy: a sketching interface for 3D freeform design," in Proceedings of the 26th annual conference on Computer graphics and interactive techniques, 1999, pp. 409-416.        [2] Z. Lun, M. Gadelha, E. Kalogerakis, S. Maji, and R. Wang, "3D shape reconstruction from sketches via multi-view convolutional networks," in 3D Vision (3DV), 2017 International Conference on, 2017, pp. 67-77.        [3] J. Delanoy, M. Aubry, P. Isola, A. Efros, and A. Bousseau, "3D Sketching using Multi-View Deep Volumetric Prediction," Proceedings of the ACM on Computer Graphics and Interactive Techniques, vol. 1, no. 21, May 2018.        [4] B. Xu, W. Chang, A. Sheffer, A. Bousseau, J. McCrae, and K. Singh, "True2Form: 3D curve networks from 2D sketches via selective regularization," ACM Transactions on Graphics, vol. 33, no. 4,2014.        [5] C. Li, H. Pan, Y. Liu, X. Tong, A. Sheffer, and W. Wang, "BendSketch: modeling freeform surfaces through 20 sketching," ACM Transactions on Graphics, vol. 36, no. 4, pp. 1-14, July 2017.        [6] Y. Zheng, H. Liu, J. Dorsey, and N. J. Mitra, "SmartCanvas: Context-inferred Interpretation of Sketches for Preparatory Design Studies," in Computer Graphics Forum, 2016, vol. 35, pp. 37-48.        [7] Y. Li, X. Luo, Y. Zheng, P. Xu, and H. Fu, "SweepCanvas: Sketch-based 3D Prototyping on an RGB-D Image," in Proceedings of the 30th Annual ACM Symposium on User Interface Software and Technology, 2017, pp. 387-399.
Papers [1] to [3] provide approaches to generate a 3D mesh from a sketch.
A main drawback of meshes is that they are hardly editable and provide no semantics. A 3D mesh discretizes a surface as a collection of basic polygons (often triangles). If the surface is watertight and manifold, it can represent a solid. Such a representation is not adapted for 3D modelling, as triangles should be edited one by one.
In addition, paper [1]'s approach generates round-like meshes. Furthermore, the approach of paper [1] requires sketch strokes to be annotated with an associated action (creation, extrusion, bending).
Paper [2] and paper [3] avoid this round-like shape priors as well as the necessity of annotated strokes thanks to recent advantages in deep learning.
However, both approaches still output a mesh. In addition, paper [2] requires one or several sketches of the object from a canonical point of view (i.e. front, side, top), which is a strong limitation for users.
Papers [4] to [7] provide approaches to generate parametric surfaces from sketches.
Paper [4] generates curves by enforcing some regularities on the sketch strokes (orthogonality, parallelism, coplanarity). Afterwards, surfaces may be fitted to the curves. This approach requires the user to be quite accurate during sketching: the strokes must represent the geometry of the object (following its surfaces but not necessarily its contours) and occluded strokes may be needed. Moreover, the user must specify the actual 3D intersection between strokes.
Paper [5] directly fits surfaces to the sketches. However, sketch strokes must be labelled. The labels provide some information about the surface that the sketch strokes should lie on: limit of the surface, concavity/convexity, sharp edge. Because of the nature of those labels, the user must be an expert in geometry, as a simple perspective sketch of the object will not be enough.
Thus, paper [4] and paper [5] provide solutions that fit a parametric surface to the input drawing, but the resulting surfaces are not necessarily closed, and as a consequence, they may not represent a solid. Even if they represent a solid, they cannot be edited as a meaningful solid CAD feature. Moreover, both methods require additional user inputs (intersections or stroke labelling).
Paper [6] generates 3D curves from sketch strokes. This approach makes the assumption that each stroke represents a planar 3D curve. Once the plane is identified, the 3D curve is obtained by back-projecting the stroke from the 2D sketch to the plane the stroke should lie on. Strokes lying on the same plane may intersect each other and define the boundaries of a planar surface patch. The obtained planar patches may be then extruded in the perpendicular direction. A main drawback of this approach is that plane orientations are limited to the three canonical orientations of the orthogonal reference frame. In order to define this reference frame, the user is required to explicit two sets of parallel lines, the first set of lines being orthogonal to the second one. Then, the reference frame is inferred form the vanishing points.
Paper [7] proposes a very similar approach. However, the proposed approach needs a depth image in addition to a classical RGB image. Stroke planes are directly estimated from the 3D of the scene provided by the depth map.
Thus, paper [6] and paper [7] provide techniques that produce results including a surface that may be extruded. However, both approaches suppose that the base 2D sketch lies on a restricted set of planes. In addition, both methods require additional inputs: pictures, user-definition of parallel lines, depth images.
Within this context, there is still a need for improved solutions for inference, from a freehand drawing representing a 3D shape, of a 3D modeled object representing the 3D shape.

Forming a dataset for inference of solid CAD features


A composite comprising:

The present invention relates to composites which are suitable for, inter alia, electrochemical cells having electrolytes containing lithium ions; their use as, for example, lithium ion batteries, batteries, sensors, electrochromic windows, displays, capacitors and ion-conducting films comprising such a composite.
Electrochemical, in particular rechargeable, cells are generally known, for example from xe2x80x9cUllmann""s Encyclopedia of Industrial Chemistryxe2x80x9d, 5th Ed., Vol. A3, VCH Verlagsgesellschaft mbH, Weinheim, 1985, pages 343-397.
Among these cells, a special position is occupied by lithium batteries and lithium ion batteries, in particular as secondary cells, owing to their high specific energy storage density.
As described, for example, in the above citation from xe2x80x9cUllmannxe2x80x9d, the cathode of such cells comprises lithiated manganese, cobalt, vanadium or nickel mixed oxides which in the stoichiometrically simplest case can be described as LiMn2O4, LiCoO2, LiV2O5 or LiNiO2.
These mixed oxides react reversibly with compounds which can incorporate lithium ions into their lattice, for example graphite, with the lithium ions being removed from the crystal lattice and the metal ions such as manganese, cobalt or nickel ions present in the latter being oxidized. This reaction can be utilized in an electrochemical cell for storing electrical energy by separating the compound which takes up lithium ions, i.e. the anode material, and the lithium-containing mixed oxide, i.e. the cathode material, by means of an electrolyte through which the lithium ions migrate from the mixed oxide into the anode material (charging operation).
The compounds suitable for the reversible storage of lithium ions are usually fixed on collector electrodes by means of a binder.
When the cell is charged, electrons flow through an external voltage source and lithium cations flow through the electrolyte to the anode material. When the cell is used, the lithium cations flow through the electrolyte whereas the electrons flow through a load from the anode material to the cathode material.
To avoid a short circuit within the electrochemical cell, a layer which is electrically insulating but permeable to lithium cations is located between the two electrodes. This layer can be a solid electrolyte or a conventional separator.
In the production of many electrochemical cells, e.g. a lithium ion battery in the form of a round cell, the necessary battery films, i.e. cathode, anode and separator films, are combined using a rolling apparatus to produce a battery roll. In conventional lithium ion batteries, the cathode and anode film(s) are joined to collector electrodes in the form of, for example, an aluminum or copper foil. Such metal foils ensure sufficient mechanical stability.
In contrast, the separator film has to withstand the mechanical stresses on its own, which presents no problem in the case of conventional separator films based on, for example, polyolefins and having the conventional thickness. To further improve the mechanical stability of such conventional separator films, JP 09-134 730 and JP 09-161 815 propose joining these separator films to the anode and/or cathode film by means of a bonding layer.
In contrast to conventional separator films, the mechanical stability of separator films filled with a solid is generally not sufficient to ensure problem-free rolling of the films.
A composite which is able to withstand the mechanical stresses occurring in the manufacture of, for example, batteries is described in WO 99/19917 by the applicant. The composite claimed there comprises at least one layer which is filled with a solid, e.g. a separator layer, and at least one second layer which can be a cathode layer or an anode layer.
It is an object of the present invention to develop the composite claimed in WO 99/19917 further and to provide a composite which can be used directly as an electrochemical cell, in particular as a lithium ion battery, and can accordingly be introduced directly into an appropriate housing for such a cell or such a battery.
The present invention accordingly provides, in one embodiment, a composite comprising
Aa) at least one separator layer Aa which comprises a mixture Ia, comprising a mix IIa consisting of
a) from 1 to 95% by weight of a solid III, preferably a basic solid III, having a primary particle size of from 5 nm to 20 xcexcm and
b) from 5 to 99% by weight of a polymeric composition IV obtainable by polymerization of
b1) from 5 to 100% by weight, based on the composition IV, of a condensation product V of
xcex1) at least one compound VI which is able to react with a carboxylic acid or a sulfonic acid or a derivative or a mixture of two or more thereof, and
xcex2) at least 1 mol per mol of the compound VI of a carboxylic acid or sulfonic acid VII which contains at least one free-radically polymerizable functional group, or a derivative thereof or a mixture of two or more thereof, and
b2) from 0 to 95% by weight, based on the composition IV, of a further compound VIII having a mean molecular weight (number average) of at least 5000 and polyether segments in the main chain or a side chain,
xe2x80x83where the proportion by weight of the mix IIa in the mixture Ia is from 1 to 100% by weight,
xe2x80x83and the layer is free of an electron-conducting, electrochemically active compound, and
B) at least one cathode layer B which comprises an electron-conducting, electrochemically active compound which is able to release lithium ions on charging,
C) at least one anode layer C which comprises an electron-conducting, electrochemical compound which is able to take up lithium ions on charging.
The separator layer or layers Aa preferably comprise(s) a mixture Ia comprising a mix IIa consisting of
a) from 1 to 95% by weight of a solid III, preferably a basic solid III, having a primary particle size of from 5 nm to 20 xcexcm and
b) from 5 to 99% by weight of a polymeric composition IV obtainable by polymerization of
b1) from 5 to 100% by weight, based on the composition IV, of a condensation product V of
xcex1) a polyhydric alcohol VI which has carbon and oxygen atoms in the main chain, and
xcex2) at least 1 mol per mol of the polyhydric alcohol VI of a xcex1,xcex2-unsaturated carboxylic acid VII, and
b2) from 0 to 95% by weight, based on the composition IV, of a further compound VIII having a mean molecular weight (number average) of at least 5000 and polyether segments in the main chain or a side chain,
xe2x80x83where the proportion by weight of the mix IIa in the mixture Ia is from 1 to 100% by weight.
In a further embodiment, the present invention provides a composite comprising
Ab) at least one first separator layer Ab which comprises a mixture Ib comprising a mix IIb consisting of
a) from 1 to 95% by weight of a solid III, preferably a basic solid, having a primary particle size of from 5 nm to 20 xcexcm and
b) from 5 to 99% by weight of a polymer IX obtainable by polymerization of
b1) from 5 to 75% by weight, based on the polymer IX, of a free-radically polymerizable compound X which is different from the carboxylic acid or the sulfonic acid VII or a derivative thereof, or a mixture of two or more thereof, and
b2) from 25 to 95% by weight, based on the polymer IX, of a further compound VIII having a mean molecular weight (number average) of at least 5000 and polyether segments in the main chain or a side chain,
xe2x80x83where the proportion by weight of the mix IIb in the mixture Ib is from 1 to 100% by weight
xe2x80x83and the layer is free of an electron-conducting, electrochemically active compound, and
xe2x80x83at least one cathode layer B and at least one anode layer C, each as defined above.
The present invention further provides a composite comprising
at least one separator layer Aa or at least one separator layer Ab or at least one separator layer Aa and at least one separator layer Ab,
at least one cathode layer B,
at least one anode layer C,
each as defined above, and
D) at least one bonding layer D.
The respective layers of the composite of the present invention, which is preferably in the form of a film, are described in more detail below.
Separator Layer Aa/Ab
The term xe2x80x9csolid IIIxe2x80x9d encompasses all compounds which are solid under normal conditions and, during operation of the battery, can neither take up nor release electrons under the conditions prevailing during charging of batteries, in particular lithium ion batteries. Such solids are for the purposes of the present invention distinguished from the xe2x80x9celectron-conducting, electrochemically activexe2x80x9d compounds in the anode or cathode layer.
The solid III used in this layer is, first and foremost, an inorganic solid, preferably an inorganic basic solid, selected from the group consisting of oxides, mixed oxides, silicates, sulfates, carbonates, phosphates, nitrides, amides, imides and carbides of the elements of main groups I, II, III and IV and transition group IV of the Periodic Table; a polymer selected from the group consisting of polyethylene, polypropylene, polystyrene, polytetrafluoroethylene, polyvinylidene fluoride, polyamides, polyimides; a solids dispersion comprising such a polymer; and a mixture of two or more thereof.
Examples which may be mentioned are, in particular: oxides such as calcium oxide, silicon dioxide, aluminum oxide, magnesium oxide or titanium dioxide, mixed oxides, for example of the elements silicon, calcium, aluminum, magnesium, titanium; silicates such as ladder, chain, sheet and framework silicates, preferably wollastonite, in particular hydrophobicized wollastonite, sulfates such as alkali metal and alkaline earth metal sulfates; carbonates such as alkali metal and alkaline earth metal carbonates, e.g. calcium, magnesium or barium carbonate or lithium, potassium or sodium carbonate; phosphates such as apatites; nitrides; amides; imides; carbides; polymers such as polyethylene, polypropylene, polystyrene, polytetrafluoroethylene, polyvinylidene fluoride; polyamides; polyimides; or other thermoplastics, thermosets, microgels, solids dispersions, in particular those comprising the abovementioned polymers, and also mixtures of two or more of the abovementioned solids.
Furthermore, inorganic solids which conduct Li ions, preferably an inorganic basic solid which conducts Li ions, can be used according to the invention as solid III.
Examples are: lithium borates such as Li4B6O11*xH2O, Li3(BO2)3, Li2B4O7*xH2O, LiBO2, where x can be from 0 to 20; lithium aluminates such as Li2O*Al2O3*H2O, Li2Al2O4, LiAlO2; lithium aluminosilicates such as lithium-containing zeolites, feldspars, feldspar substitutes, phyllosilicates and inosilicates, and, in particular, LiAlSi2O6 (spodumene), LiAlSi4O10 (petullite), LiAlSiO4 (eucryptite), mica such as K[Li,Al]3[AlSi]4O10(Fxe2x80x94OH)2,/K[Li,Al,Fe]3[AlSi]4O10(Fxe2x80x94OH)2; lithium zeolites, in particular those in fiber, sheet or cube form, in particular those having the formula Li2/zO*Al2O3*xSiO2*yH2O, where z corresponds to the valence, x is from 1.8 to about 12 and y is from 0 to about 8; lithium carbides such as Li2C2, Li4C; Li3N; lithium oxides and mixed oxides such as LiAlO2, Li2MnO3, Li2O, Li2O2, Li2MnO4, Li2TiO3; Li2NH; LiNH2; lithium phosphates such as Li3PO4, LiPO3, LiAlFPO4, LiAl(OH)PO4, LiFePO4, LiMnPO4; Li2CO3; lithium silicates in ladder, chain, sheet and framework form, e.g. Li2SiO3, Li2SiO4 and Li6Si2; lithium sulfates such as Li2SO4, LiHSO4, LiKSO4; the Li compounds mentioned in the discussion of the cathode layer, with the presence of conductive black being ruled out when they are used as solid III; and also mixtures of two or more of the abovementioned solids which conduct Li ions.
Particularly suitable solids III are basic solids. For the purposes of the present invention, basic solids are those whose mixture with a liquid, water-containing diluent which itself has a pH of at most 7 has a higher pH than this diluent.
The solids are preferably very largely insoluble in the liquid used as electrolyte and electrochemically inert in the battery medium.
Particularly suitable solids are those which have a primary particle size of from 5 nm to 20 xcexcm, preferably from 0.01 to 10 xcexcm and in particular from 0.1 to 5 xcexcm, where the particle sizes specified are determined by electron microscopy. The melting point of the solid is preferably above the operating temperature customary for the electrochemical cell; melting points of above 120xc2x0 C., in particular above 150xc2x0 C., have been found to be particularly useful.
In terms of their external shape, the solids can be symmetrical, i.e. have an aspect ratio height:width:length of about 1 and be in the form of spheres, granules, approximately round structures, but also in the form of any polyhedra such as cuboids, tetrahedra, hexahedra, octahedra or bipyramids, or can be distorted or asymmetric, i.e. have an aspect ratio height:width:length different from 1 and be in the form of needles, asymmetric tetrahedra, asymmetric bipyramids, asymmetric hexahedra or octahedra, platelets, disks or as fibers. If the solids are in the form. of asymmetric particles, the abovementioned upper limit for the primary particle size relates in each case to the smallest axis.
As compound VI which is able to react with a carboxylic acid or a sulfonic acid VII or a derivative or a mixture of two or more thereof, it is possible in principle to use all compounds which fulfill this criterion.
The compound VI is preferably selected from the group consisting of monohydric or polyhydric alcohols having only carbon atoms in the main chain; monohydric or polyhydric alcohols whose main chain comprises at least two carbon atoms plus at least one atom selected from the group consisting of oxygen, phosphorus and nitrogen; silicon-containing compounds; amines having at least one primary amino group; amines having at least one secondary amino group; aminoalcohols; monohydric or polyhydric thiols; compounds containing at least one thiol group and at least one hydroxyl group; and mixtures of two or more thereof.
Among these, preference is in turn given to compounds VI containing two or more functional groups which can react with the carboxylic acid or sulfonic acid.
When compounds VI containing amino groups as functional group are used, preference is given to using those having secondary amino groups so that after condensation/crosslinking there are either absolutely no free NH groups or only small amounts thereof present in the mixture Ia.
Specific examples of preferred compounds are:
monohydric or polyhydric alcohols which have only carbon atoms in the main chain and have from 1 to 20, preferably from 2 to 20 and in particular from 2 to 10, alcoholic OH groups, in particular dihydric, trihydric and tetrahydric alcohols, preferably having from 2 to 20 carbon atoms, e.g. ethylene glycol, 1,2- or 1,3-propanediol, 1,2- or 1,3-butanediol, 1,4-butenediol or 1,4-butynediol, 1,6-hexanediol, neopentyl glycol, 1,2-dodecanediol, glycerol, trimethylolpropane, pentaerythritol or sugar alcohols, hydroquinone, novolak, bisphenol A; it is also possible, as can be seen from the above definition, to use monohydric alcohols such as methanol, ethanol, propanol, n-, sec- or tert-butyl, etc.; use can also be made of polyhydroxyolefins, preferably those having two terminal hydroxyl groups, e.g. xcex1,xcfx89-dihydroxybutadiene;
polyester polyols as are known, for example, from Ullmanns Encyclopxc3xa4die der technischen Chemie, 4th edition, Volume 19, pp. 62-65 and are obtained, for example, by reaction of dihydric alcohols with polybasic, preferably dibasic, polycarboxylic acids;
monohydric or polyhydric alcohols whose main chain comprises at least two carbon atoms plus at least one oxygen atom, preferably polyether alcohols such as polymerization products of alkylene epoxides, for example isobutylene oxide, propylene oxide, ethylene oxide, 1,2-epoxybutane, 1,2-epoxypentane, 1,2-epoxyhexane, tetrahydrofuran, styrene oxide; use can also be made of polyether alcohols which are modified at the end groups, e.g. polyether alcohols modified by NH2 end groups; these alcohols preferably have a molecular weight (number average) of from 100 to 5000, more preferably from 200 to 1000 and in particular from 300 to 800; such compounds are known per se and are commercially available, for example under the trade names Pluriol(copyright) or Pluronic(copyright) (BASF Aktiengesellschaft);
alcohols as defined above in which some or all carbon atoms are replaced by silicon; compounds of this type which can be used are, in particular, polysiloxanes or alkylene oxide-siloxane copolymers or mixtures of polyether alcohols and polysiloxanes as are described, for example, in EP-B 581 296 and EP-A 525 728; as regards the molecular weight of these alcohols, what has been said above also applies;
alcohols as defined above, in particular polyether alcohols, in which some or all oxygen atoms are replaced by sulfur atoms; with regard to the molecular weight of these alcohols, what has been said above likewise applies;
monohydric or polyhydric alcohols whose main chain comprises at least two carbon atoms plus at least one phosphorus atom or at least one nitrogen atom, e.g. diethanolamine and triethanolamine;
lactones which are derived from compounds of the formula HOxe2x80x94(CH2)zxe2x80x94COOH, where z is from 1 to 20, e.g. xcex5-caprolactone, xcex2-propiolactone, xcex3-butyrolactone or methyl-xcex5-caprolactone;
silicon-containing compounds such as dichlorosilane or trichlorosilane, phenyltrichlorosilane, diphenyldichlorosilane, dimethylvinylchlorosilane;
silanols such as trimethylsilanol;
amines having at least one primary and/or secondary amino group, e.g. butylamine, 2-ethylhexylamine, ethylenediamine, hexamethylenediamine, diethylenetriamine, tetraethylenepentamine, pentaethylenehexamine, aniline, phenylenediamine;
polyetherdiamines such as 4,7-dioxydecane-1,10-diamine, 4,11-dioxytetradecane-1,14-diamine;
monohydric or polyhydric thiols, e.g. aliphatic thiols such as methanethiol, ethanethiol, cyclohexanethiol, dodecanethiol; aromatic thiols such as thiophenol, 4-chlorothiophenol, 2-mercaptoaniline;
compounds containing at least one thiol group and at least one hydroxyl group, e.g. 4-hydroxythiophenol and monothio derivatives of the abovementioned polyhydric alcohols;
amino alcohols such as ethanolamine, N-methylethanolamine, N-ethylethanolamine, N-butylethanolamine, 2-amino-1-propanol, 2-amino-1-phenylethanol, monoamino or polyamino polyols having more than two aliphatically bound hydroxyl groups, e.g. tris(hydroxymethyl)methylamine, glucamine, N,Nxe2x80x2-bis(2-hydroxymethyl)ethylenediamine.
It is also possible to use mixtures of two or more of the above-defined compounds VI.
According to the present invention, the abovementioned compounds VI are condensed with a carboxylic acid or sulfonic acid VII which contains at least one free-radically polymerizable functional group or a derivative thereof or a mixture of two or more thereof, in which reaction at least one, preferably all, of the free groups capable of condensation within the compounds VI are condensed with the compound VII.
Carboxylic acids or sulfonic acids VII which can be used for the purposes of the present invention are in principle all carboxylic and sulfonic acids which contain at least one free-radically polymerizable functional group, and also their derivatives. The term xe2x80x9cderivativesxe2x80x9d used here encompasses both compounds which are derived from a carboxylic or sulfonic acid and in which the acid function is modified, e.g. esters, acid halides or acid anhydrides, and compounds which are derived from a carboxylic or sulfonic acid and in which the carbon skeleton of the carboxylic or sulfonic acid is modified, e.g. halocarboxylic or halosulfonic acids.
Examples of compound VII are, in particular:
xcex1,xcex2-unsaturated carboxylic acids or xcex1,xcex3-unsaturated carboxylic acids.
Particularly suitable xcex1,xcex2-unsaturated carboxylic acids are those of the formula
where
R1, R2 and R3 are hydrogen or C1-C4-alkyl radicals; among these, preference is in turn given to acrylic acid and methacrylic acid; other suitable compounds are cinnamic acid, maleic acid, fumaric acid, itaconic acid or p-vinylbenzoic acid, and also derivatives thereof, e.g. anhydrides such as maleic anhydride or itaconic anhydride;
halides, in particular chlorides, such as acryloyl or methacryloyl chloride; esters such as (cyclo)alkyl(meth)acrylates having up to 20 carbon atoms in the alkyl radical, e.g. methyl, ethyl, propyl, butyl, hexyl, 2-ethylhexyl, stearyl, lauryl, cyclohexyl, benzyl, trifluoromethyl, hexafluoropropyl or tetrafluoropropyl(meth)acrylate, polypropylene glycol mono(meth)acrylates, polyethylene glycol mono(meth)acrylates, poly(meth)acrylates of polyhydric alcohols, e.g. glyceryl di(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythrityl di- or tri-(meth)acrylate, diethylene glycol bis(mono(2-acryloxyethyl)carbonate), poly(meth)acrylates of alcohols which themselves in turn contain a free-radically polymerizable group, e.g. esters of (meth)acrylic acid and vinyl and/or allyl alcohol;
vinyl esters of other aliphatic or aromatic carboxylic acids, e.g. vinyl acetate, vinyl propionate, vinyl butyrate, vinyl hexanoate, vinyl octanoate, vinyl decanoate, vinyl stearate, vinyl palmitate, vinyl crotonate, divinyl adipate, divinyl sebacate, vinyl 2-ethylhexanoate, vinyl trifluoroacetate;
allyl esters of other aliphatic or aromatic carboxylic acids, e.g. allyl acetate, allyl propionate, allyl butyrate, allyl hexanoate, allyl octanoate, allyl decanoate, allyl stearate, allyl palmitate, allyl crotonate, allyl salicylate, allyl lactate, diallyl oxalate, diallyl malonate, diallyl succinate, diallyl glutarate, diallyl adipate, diallyl pimelate, diallyl cinnatricarboxylate, allyl trifluoroacetate, allyl perfluorobutyrate, allyl perfluorooctanoate;
xcex2,xcex3-unsaturated carboxylic acids or their derivatives, e.g. vinylacetic acid, 2-methylvinylacetic acid, isobutyl 3-butenoate, allyl 3-butenoate, allyl 2-hydroxy-3-butenoate, diketene;
sulfonic acids such as vinylsulfonic acid, allylsulfonic and methylylsulfonic acids, and also their esters and halides, vinyl benzenesulfonate, 4-vinylbenzenesulfonamide.
It is also possible to use mixtures of two or more of the above-described carboxylic and/or sulfonic acids.
Specific examples of compound X which is capable of free-radical polymerization and can be used for preparing the polymer IX are:
olefinic hydrocarbons such as ethylene, propylene, butylene, isobutene, hexene or higher homologues and vinylcyclohexane;
(meth)acrylonitrile;
halogen-containing olefinic compounds such as vinylidene fluoride, vinylidene chloride, vinyl fluoride, vinyl chloride, hexafluoropropene, trifluoropropene, 1,2-dichloroethylene, 1,2-difluoroethylene and tetrafluoroethylene;
vinyl alcohol, vinyl acetate, N-vinylpyrrolidone, N-vinylimidazole, vinylformamide;
phosphonitrilic chlorides such as hexachloro(triphosphazene), and also derivatives thereof which are partially or completely substituted by alkoxy, phenoxy, amino and fluoroalkoxy groups, i.e. compounds which can be polymerized to form polyphosphazenes;
aromatic, olefinic compounds such as styrene, xcex1-methylstyrene;
vinyl ethers such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, decyl, dodecyl, 2-ethylhexyl, cyclohexyl, benzyl, trifluoromethyl, hexafluoropropyl and tetrafluoropropyl vinyl ether.
It is, of course, also possible to use mixtures of the above compounds X, resulting in copolymers in which the monomers are, depending on the method of preparation, distributed randomly or arranged in blocks.
Preference is here given to using polymers and copolymers of vinyl chloride, acrylonitrile, vinylidene fluoride, vinyl chloride and vinylidene chloride, vinyl chloride and acrylonitrile, vinylidene chloride with hexafluoropropylene, vinylidene fluoride with hexafluoropropylene and a member selected from the group consisting of vinyl fluoride, tetrafluoroethylene and a trifluoroethylene, as are described, for example, in U.S. Pat. No. 5,540,741 and U.S. Pat. No. 5,478,668 whose disclosures in this respect are fully incorporated by reference into the present application. Among these, preference in turn is given to copolymers of vinylidene fluoride (1,1-difluoroethene) and hexafluoropropene, more preferably random copolymers of vinylidene fluoride and hexafluoropropene, in which the proportion by weight of vinylidene fluoride is from 75 to 92% and that of hexafluoropropene is from 8 to 25%.
Both these compounds X and the condensation products V are polymerized by conventional methods well known to those skilled in the art, preferably polymerized by a free-radical mechanism; as regards the molecular weights obtained, what is said below for the compound VIII applies.
Suitable compounds VIII are, first and foremost, compounds having a mean molecular weight (number average) of at least 5000, preferably from 5000 to 20,000,000, in particular from 100,000 to 6,000,000, which are able to solvate lithium cations and function as binders. Examples of suitable compounds VIII are polyethers and copolymers which comprise at least 30% by weight of the following structural unit, based on the total weight of the compound VIII:
where
R1, R2, R3 and R4 are aryl groups, alkyl groups, preferably methyl groups, or hydrogen and can be identical or different and contain heteroatoms such as oxygen, nitrogen, sulfur or silicon.
Such compounds are described, for example, in: M. B. Armand et. al., Fast Ion Transport in Solids, Elsevier, N.Y., 1979, pp. 131-136, or in FR-A 7832976.
The compound VIII can also consist of a mixture of two or more such compounds.
The above-defined polymeric composition IV or the polymer IX can also be in the form of a foam, in which case the solid III is present as a dispersion therein.
The mixes IIa should, according to the present invention, consist of from 1 to 95% by weight, preferably from 25 to 90% by weight and in particular from 30 to 70% by weight, of a solid III and from 5 to 99% by weight, preferably from 10 to 75% by weight and in particular from 30 to 70% by weight, of a polymeric composition IV, and the compound VIII of the polymeric composition IV should advantageously have a mean molecular weight (number average) of from 5000 to 100,000,000, preferably from 50,000 to 8,000,000. The polymeric composition IV can be obtained by reacting from 5 to 100% by weight, preferably from 30 to 70% by weight, based on the polymeric composition IV, of a compound V with from 0 to 95% by weight, in particular from 30 to 70% by weight, based on the polymeric composition IV, of a compound VIII.
The mixes IIb should, according to the present invention, consist of from 1 to 95% by weight, preferably from 25 to 90% by weight and in particular from 30 to 70% by weight, of a solid III and from 5 to 99% by weight, preferably from 10 to 75% by weight and in particular from 30 to 70% by weight, of a polymer IX, and the compound VIII of the polymer IX should advantageously have a mean molecular weight (number average) of from 5000 to 100,000,000, preferably from 50,000 to 8,000,000. The polymer IX can be obtained by reacting from 5 to 75% by weight, preferably from 30 to 70% by weight, based on the polymer IX, of a compound X with from 25 to 95% by weight, in particular from 30 to 70% by weight, based on the polymer IX, of a compound VIII.
In the following, the mixtures Ia and Ib used according to the present invention and the mixes IIa and IIb used according to the present invention are discussed together and referred to as xe2x80x9cmixture used according to the present inventionxe2x80x9d and xe2x80x9cmix used according to the present inventionxe2x80x9d respectively.
To prepare the mixture used according to the present invention which should comprise a mix used according to the present invention in an amount of from 1 to 100% by weight, preferably from 35 to 100% by weight and in particular form 30 to 70% by weight, based on the mixture used according to the present invention, a mixture of a solid III, a condensation product V and, if desired, a compound VIII or a mixture of a solid III, a compound X, a compound VIII and customary additives such as plasticizers, preferably plasticizers comprising polyethylene oxide or polypropylene oxide, can be prepared.
Anode Layer B and Cathode Layer C
As polymeric binder in these layers B and C, use is made of the following polymers. The polymeric binders used in the layers B and C can be identical or different from one another. Particular mention may be made of:
1) Homopolymers, copolymers or block copolymers IVa (polymers IVa) obtainable by polymerization of the above-defined mixtures Ia or Ib.
2) Polycarbonates such as polyethylene carbonate, polypropylene carbonate, polybutadiene carbonate, polyvinylidene carbonate.
3) Homopolymers, copolymers and block copolymers prepared from
a) olefinic hydrocarbons such as ethylene, propylene, butylene, isobutene, propene, hexene or higher homologues, butadiene, cyclopentene, cyclohexene, norbomene, vinylcyclohexane;
b) aromatic hydrocarbons such as styrene and methylstyrene;
c) esters of acrylic acid or methacrylic acid, e.g. methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, decyl, dodecyl, 2-ethylhexyl, cyclohexyl, benzyl, trifluoromethyl, hexafluoropropyl or tetrafluoropropyl acrylate or methacrylate;
d) acrylonitrile, methacrylonitrile, N-methylpyrrolidone, N-vinylimidazole, vinyl acetate;
e) vinyl ethers such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, decyl, dodecyl, 2-ethylhexyl, cyclohexyl, benzyl, trifluoromethyl, hexafluoropropyl or tetrafluoropropyl vinyl ether;
f) halogen-containing olefinic compounds such as vinyl chloride, vinyl fluoride, vinylidene fluoride, vinylidene chloride, hexafluoropropene, trifluoropropene, 1,2-dichloroethene, 1,2-difluoroethene, tetrafluoroethene.
4) Polyurethanes, for example obtainable by reacting
a) organic diisocyanates having from 6 to 30 carbon atoms, for example aliphatic acyclic diisocyanates such as hexamethylene 1,5-diisocyanate and hexamethylene 1,6-diisocyanate, aliphatic cyclic diisocyanates such as cyclohexylene 1,4-diisocyanate, dicyclohexylmethane diisocyanate and isophorone diisocyanate or aromatic diisocyanates such as tolylene 2,4-diisocyanate, tolylene 2,6-diisocyanate, m-tetramethylxylene diisocyanate, p-tetramethylxylene diisocyanate, tetrahydronaphthylene 1,5-diisocyanate and diphenylmethane 4,4xe2x80x2-diisocyanate or mixtures of such compounds, with
b) polyhydric alcohols such as polyesterols, polyetherols and diols.
xe2x80x83The polyesterols are advantageously predominantly linear polymers having terminal OH groups, preferably those having two or three, in particular two, OH end groups. The acid number of the polyesterols is less than 10 and preferably less than 3. The polyesterols can be prepared in a simple manner by esterification of aliphatic or aromatic dicarboxylic acids having from 4 to 15 carbon atoms, preferably from 4 to 6 carbon atoms, with glycols, preferably glycols having from 2 to 25 carbon atoms, or by polymerization of lactones having from 3 to 20 carbon atoms. Examples of dicarboxylic acids which can be used are glutaric acid, pimelic acid, suberic acid, sebacic acid, dodecanoic acid and preferably adipic acid and succinic acid. Suitable aromatic dicarboxylic acids are terephthalic acid, isophthalic acid, phthalic acid or mixtures of these dicarboxylic acids with other dicarboxylic acids, e.g. diphenic acid, sebacic acid, succinic acid and adipic acid. The dicarboxylic acids can be used individually or as mixtures. To prepare the polyesterols, it may be advantageous to use the corresponding acid derivatives such as carboxylic anhydrides or carboxylic chlorides in place of the dicarboxylic acids. Examples of suitable glycols are diethylene glycol, 1,5-pentanediol, 1,10-decanediol and 2,2,4-trimethylpentane-1,5-diol. Preference is given to using 1,2-ethanediol, 1,3-propanediol, 2-methylpropane-1,3-diol, 1,4-butanediol, 1,6-hexanediol, 2,2-dimethylpropane-1,3-diol, 1,4-dimethylolcyclohexane, 1,4-diethanolcyclohexane and ethoxylated or propoxylated products of 2,2-bis(4-hydroxyphenyl)propane (bisphenol A). Depending on the desired properties of the polyurethanes, the polyols can be used alone or as a mixture in various mixing ratios. Suitable lactones for preparing the polyesterols are, for example, xcex1,xcex1-dimethyl-xcex2-propiolactone, xcex3-butyrolactone and preferably xcex5-caprolactone.
xe2x80x83The polyetherols are essentially linear substances having terminal hydroxyl groups and containing ether bonds. Suitable polyetherols can easily be prepared by polymerization of cyclic ethers such as tetrahydrofuran or by reacting one or more alkylene oxides having from 2 to 4 carbon atoms in the alkylene radical with an initiator molecule containing two active hydrogen atoms in bound form in the alkylene radical. Examples of suitable alkylene oxides are ethylene oxide, 1,2-propylene oxid, epichlorohydrin, 1,2-butylene oxide and 2,3-butylene oxide. The alkylene oxides can be used individually, alternately in succession or as a mixture. Suitable initiator molecules are, for example, water, glycols such as ethylene glycol, propylene glycol, 1,4-butanediol and 1,6-hexanediol, amines such as ethylenediamine, hexamethylenediamine and 4,4xe2x80x2-diaminodiphenylmethane and aminoalcohols such as ethanolamine. Suitable polyesterols and polyetherols and their preparation are described, for example, in EP-B 416 386; suitable polycarbonatediols, preferably those based on 1,6-hexanediol, and their preparation are described, for example, in U.S. Pat. No. 4,131,731.
xe2x80x83Use can advantageously be made of up to 30% by weight, based on the total mass of the alcohols, of aliphatic diols having from 2 to 20, preferably from 2 to 10, carbon atoms, e.g. 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol, 1,5-pentanediol, 1,10-decanediol, 2-methylpropane-1,3-diol, 2,2-dimethylpropane-1,3-diol, 2-methyl-2-butylpropane-1,3-diol, 2,2-dimethylbutane-1,4-diol, 1,4-dimethylolcyclohexane, neopentyl glycol hydroxypivalate, diethylene glycol, triethylene glycol and methyldiethanolamine or aromatic-aliphatic or aromatic-cycloaliphatic diols having from 8 to 30 carbon atoms where possible aromatic structures are heterocyclic ring systems or preferably isocyclic ring systems, for example naphthalene or, in particular, benzene derivatives such as bisphenol A, symmetrically diethoxylated bisphenol A, symmetrically dipropoxylated bisphenol A, higher ethoxylated or propoxylated bisphenol A derivatives or bisphenol F derivatives, and also mixtures of such compounds.
xe2x80x83Use can advantageously be made of up to 5% by weight, based on the total mass of the alcohols, of aliphatic triols having from 3 to 15, preferably from 3 to 10, carbon atoms, for example trimethylolpropane or glycerol, the reaction product of such compounds with ethylene oxide and/or propylene oxide, and also mixtures of such compounds.
xe2x80x83The polyhydric alcohols may bear functional groups, for example neutral groups such as siloxane groups, basic groups such as, in particular, tertiary amino groups or acid groups or their salts or groups which are easily converted into acid groups; these groups are introduced via a polyhydric alcohol. Preference is given to using diol components which bear such groups, e.g. N-methyldiethanolamine, diethyl N,N-bis(hydroxyethyl)aminomethylphosphonate or 3-sulfopropyl N,N-bis(hydroxyethyl)-2-aminoacetate, or dicarboxylic acids which bear such groups and can be used for the preparation of polyesterols, for example 5-sulfoisophthalic acid.
xe2x80x83Acid groups are, in particular, the phosphoric acid, phosphonic acid, sulfuric acid, sulfonic acid, carboxyl or ammonium group.
xe2x80x83Groups which are easily converted into acid groups are, for example, ester groups or salts, preferably of the alkali metals such as lithium, sodium or potassium.
5) The above-described polyesterols themselves; care should be taken to ensure that molecular weights in the range from 10,000 to 2,000,000, preferably from 50,000 to 1,000,000 are obtained.
6) Polyamines, polysiloxanes and polyphosphazenes, in particular those which have already been discussed in the description of the polymer IVb.
7) Polyetherols as have been described, for example, in the above discussion of the polymer IVa as compound IX or in the discussion of the polyurethanes.
The cathode layer C comprises an electron-conducting, electrochemically active compound customarily used for cathodes (cathode compound) which is able to take up electrons on charging, preferably a lithium compound. Particular examples which may be mentioned are:
LiCoO2, LiNiO2, LiNixCOyO2, LiNixCOyAlzO2, where 0 less than x,y,zxe2x89xa61, LixMnO2(0 less than xxe2x89xa61), LixMn2O4(0 less than xxe2x89xa62), LixMoO2(0 less than xxe2x89xa62), LixMnO3(0 less than xxe2x89xa61), LixMnO2(0 less than xxe2x89xa62), LixMn2O4(0 less than xxe2x89xa62), LixV2O4(0 less than xxe2x89xa62.5), LixV2O3(0 less than xxe2x89xa63.5), LixVO2(0 less than xxe2x89xa61), LixWO2(0 less than xxe2x89xa61), LixWO3(0 less than xxe2x89xa61), LixTiO2(0 less than xxe2x89xa61), LixTi2O4 (0 less than xxe2x89xa62), LixRuO2(0 less than xxe2x89xa61), LixFe2O3(0 less than xxe2x89xa62), LixFe3O4(0 less than xxe2x89xa62), LixCr2O3 (0 less than xxe2x89xa63), LixCr3O4(0 less than xxe2x89xa63.8), LixV3S5(0 less than xxe2x89xa61.8), LixTa2S2(0 less than xxe2x89xa61), LixFeS(0 less than xxe2x89xa61), LixFeS2(0 less than xxe2x89xa61), LixNbS2(0 less than xxe2x89xa62.4), LixMoS2(0 less than xxe2x89xa63), LixTiS2(0 less than xxe2x89xa62), LixZrS2(0 less than xxe2x89xa62), LixNbSe2(0 less than xxe2x89xa63), LixVSe2(0 less than xxe2x89xa61), LixNiPS2(0 less than xxe2x89xa61.5), LixFePS2(0 less than xxe2x89xa61.5).
The anode layer C comprises a customary electron-conducting electrochemically active compound known from the prior art (anode compound) which is able to release electrons on charging; particular examples which may be mentioned are: lithium, lithium-containing metal alloys, micronized carbon black, natural and synthetic graphite, synthetic graphitized carbon powder and carbon fibers, oxides such as titanium oxide, zinc oxide, tin oxide, molybdenum oxide, tungsten oxide, carbonates such as titanium carbonate, molybdenum carbonate and zinc carbonate.
The anode layer C further comprises up to 30% by weight, based on the total weight of materials present in it (polymeric binder plus anode compound), of conductive black and, if desired, customary additives. The cathode layer B comprises, based on the total weight of the materials present in it (polymeric binder plus cathode compound), from 0.1 to 20% by weight of conductive black.
Bonding Layer D
As bonding layer D, it is possible in principle to use all materials which are able to join the first layer or layers, as defined above, and the second layer or layers, as defined above, to one another.
The bonding layer is, in particular if the layers in question are joined to one another by hot lamination, generally a material which has a melting point which is lower, preferably from 20 to 50xc2x0 C. lower, than those of the separator layer or layers Aa/Ab or the cathode (B) or anode C layer or layers or the separator layer or layers Aa/Ab and the cathode (B) and anode C layer or layers. The melting point of these materials is generally from 25 to 250xc2x0 C., preferably from 50 to 200xc2x0 C. and in particular from 70 to 180xc2x0 C.
The bonding layer D can also comprise a solid III. The amounts of the solid correspond essentially to the amounts specified for the further layers A to C, in each case based on the material forming the bonding layer.
As such materials forming the bonding layer, it is possible to use all materials customarily used as adhesives. Of course, it has to be possible to apply these materials to the layers A and/or B by customary methods of layer formation, for example printing on, casting on, spraying on, extruding, doctor blade coating, etc.
Preference is given to using polymeric compounds as materials forming the bonding layer.
Mention may here be made of:
melt adhesives such as those based on ethylene-vinyl acetate copolymers which are generally additionally mixed with resins and/or waxes or paraffins so as to vary their melt flow index, those based on low molecular weight (co)polyethylene, atactic(co)polypropylene, ethylene-acrylic ester copolymers and styrene-butadiene and styrene-isoprene block copolymers, polyisobutylene and also poly(meth)acrylates and polyesters such as polyethylene terephthalate which can likewise in each case be mixed with plasticizers, in particular those mentioned herein, in order to vary their melt flow index;
adhesive plastisols which are essentially mixed from a dispersion of finely divided polyvinyl chloride in plasticizers and low molecular weight materials which are reactive under the action of heat and act as bonding agents, e.g. epoxy resin compounds, phenolic resins, etc;
heat-sealing adhesives such as those based on copolymers of vinyl chloride or vinylidene chloride, copolymers of vinylidene fluoride and hexafluoropropene (e.g. Kynarflex(copyright)), copolymers of vinyl acetate, polymethacrylic esters, polyurethanes and polyesters which can in turn likewise be mixed with other polymers or resins;
contact adhesives such as those based on natural rubber, synthetic rubber in admixture with resins and solutions of high molecular weight polyurethane elastomers, where the rubber components used are mostly polychloroprene, nitrile or SBR rubbers and the resins used are mainly phenolic resins, rosins and also hydrocarbon resins;
pressure sensitive adhesives such as those based on synthetic and natural rubbers, poly(meth)acrylic esters, polyvinyl ethers and polyisobutylene, in each case again in combination with modified natural resins, phenol-formaldehyde resins or hydrocarbon resins;
pressure sensitive dispersion adhesives such as those based on poly(meth)acrylic esters;
cold-curing, warm-curing (at from about 80 to about 100xc2x0 C.) and hot-curing (at from about 100 to about 250xc2x0 C.) reaction adhesives such as one-component or two-component polymerization adhesives, where the polymers used for the two-component polymerization adhesives are, in particular, synthetic rubbers such as polychloroprene, styrene-butadiene rubber, butyl rubber, polystyrene, polymethacrylates with accelerators such as those based on amines and, for example, benzoyl peroxide as hardener, and examples of one-component polymerization adhesives are those based on cyanoacrylate;
epoxy adhesives such as those based on condensation products of epichlorohydrin and polyhydric phenols such as bisphenol A;
aminoplastics; phenolic resin adhesives;
reactive polyurethane adhesives;
polymethylol compounds;
silicone adhesives; and
polyimides and polyimidazoles such as polyaminamide and polybenzimidazole.
Specific examples are:
polyethylene oxide; polyvinyl ethers such as poly(vinyl methyl ether), poly(vinyl ethyl ether), poly(vinyl propyl ether), poly(vinyl butyl ether), poly(vinyl isobutyl ether); (co)polyacrylates and (co)polymethacrylates, with preference being given to those having relatively long alkyl chains, e.g. polybutyl(meth)acrylate or polyhexyl(meth)acrylate; polyvinylpyrrolidone; polyurethanes, where the abovementioned polyurethanes can likewise be used; wax-like (co)polyolefins such as polyethylene, polypropylene and polyisoprene waxes; rubber-like materials; polyisobutylene; and also mixtures of two or more thereof.
Further details regarding the materials which can be used according to the present invention in the bonding layer may be found in an article entitled xe2x80x9cKleben und Klebestoffexe2x80x9d (Chemie in unserer Zeit, number 4 (1980), and also Ullmann, Encyklopxc3xa4die der technischen Chemie, 4th edition (1977), volume 14, pp. 227-268 and also the literature cited therein, whose contents relating to materials having adhesive properties are incorporated by reference into the present application.
In particular, the present invention provides composites having the following structure:
cathode layer B,
bonding layer D,
separator layer Aa,
further bonding layer D which can be identical to or different from the first bonding layer D, and
anode layer C,
composites having the following structure:
cathode layer B,
bonding layer D,
separator layer Aa,
further bonding layer D which can be identical to or different from the first bonding layer D,
further layer of a conventional separator,
third bonding layer D which can be identical to or different from the first and/or the second bonding layer D, and
anode layer C, and also
composites having the following structure:
cathode layer B,
bonding layer D,
further layer of a conventional separator,
further bonding layer D which can be identical to or different from the first bonding layer D,
separator layer Aa,
third bonding layer D which can be identical to or different from the first and/or the second bonding layer D, and
anode layer C,
where the cathode layers B and/or the anode layers C are preferably firmly bound to a metal layer as electron collector.
The layer of a conventional separator which can likewise be used according to the present invention includes layers of all conventional separators, where in particular the following may be mentioned:
separators based on microporous polyolefin films whose microporosity is achieved by drawing and/or leaching out of additives such as waxes; these are commercially available, for example under the trade names Celgard(copyright), Hipore(copyright), and are described, inter alia, in EP-A 0 715 364, both of which are fully incorporated by reference into the present application; polyethylene and polypropylene films and films comprising blends of polyethylene or polypropylene with further polymers are likewise well suited;
microporous polytetrafluoroethylene (PTFE) films from Goretex as are described, for example, in EP-A 0 798 791 which is likewise incorporated by reference into the present application;
felts, fibers and nonwoven textile composites, known as xe2x80x9cnonwovensxe2x80x9d, which can all be produced using fibrous polymer materials such as polyolefin, polyamide and polyester fibers;
films obtainable under the trade name Nafion(copyright).
The composite of the present invention can further comprise a plasticizer. Suitable plasticizers of this type are described in PCT/EP98/06394 and PCT/EP98/06237.
Plasticizers which are preferably used are dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, ethylene carbonate, propylene carbonate; ethers such as dibutyl ether, di-tert-butyl ether, dipentyl ether, dihexyl ether, diheptyl ether, dioctyl ether, dinonyl ether, didecyl ether, didodecyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, 1-tert-butoxy-2-methoxyethane, 1-tert-butoxy-2-ethoxyethane, 1,2-dimethoxypropane, 2-methoxyethyl ether, 2-ethoxyethyl ether, oligoalkylene oxide ethers such as diethylene glycol dibutyl ether, dimethylene glycol tert-butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, xcex3-butyrolactone, dimethylformamide; hydrocarbons of the formula CnH2n+2 where 7 less than n less than 50; organic phosphorus compounds, in particular phosphates and phosphonates such as trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, triisobutyl phosphate, tripentyl phosphate, trihexyl phosphate, trioctyl phosphate, tris(2-ethylhexyl)phosphate, tridecyl phosphate, diethyl n-butyl phosphate, tris(butoxyethyl)phosphate, tris(2-methoxyethyl)phosphate, tris(tetrahydrofuryl)phosphate, tris(1H,1H,5H-octafluoropentyl)phosphate, tris(1H,1H-trifluoroethyl)phosphate, tris(2-(diethylamino)ethyl)phosphate, diethyl ethylphosphonate, dipropyl propylphosphonate, dibutyl butylphosphonate, dihexyl hexylphosphonate, dioctyl octylphosphonate, ethyl dimethyl phosphonoacetate, methyl diethyl phosphonoacetate, triethyl phosphonoacetate, dimethyl(2-oxopropyl)phosphonate, diethyl(2-oxopropyl)phosphonate, dipropyl(2-oxopropyl)phosphonate, ethyl diethoxyphosphinylformate, trimethyl phosphonoacetate, triethyl phosphonoacetate, tripropyl phosphonoacetate, tributyl phosphonoacetate. Trialkyl phosphates and carbonates are preferred.
The plasticizer content of the respective layer is, based on the mix present therein or the material making up the layer (polymeric binder plus cathode or anode material), from 0 to 200% by weight, preferably from 0 to 100% by weight and more preferably from 0 to 70% by weight.
The starting materials used for the respective layers can be dissolved or dispersed in an inorganic or preferably organic liquid diluent, where the resulting solution should have a viscosity of preferably from 100 to 50,000 mPas, and subsequently applied in a known manner, for example by spray coating, casting, dipping, spin coating, roller coating or letterpress, gravure, planographic or screen printing or by extrusion, if desired to a support material, i.e. shaped to form a film-like structure. Further processing can be carried out in a customary way, e.g. by removing the diluent and curing the materials.
Suitable organic diluents are aliphatic ethers, in particular tetrahydrofuran and dioxane, hydrocarbons, in particular hydrocarbon mixtures such as petroleum spirit, toluene and xylene, aliphatic esters, in particular ethyl acetate and butyl acetate, and ketones, in particular acetone, ethyl methyl ketone and cyclohexanone. It is also possible to use combinations of such diluents.
Suitable support materials are the materials customarily used for electrodes, preferably metals such as aluminum and copper. It is also possible to use coated glass substrates, in particular ITO-coated glass substrates or temporary intermediate supports such as films, in particular polyester films such as polyethylene terephthalate films. Such films can advantageously be provided with a release layer, preferably of polysiloxanes.
Likewise, the production of the individual films which then form the layers within the composite of the present invention can be carried out thermoplastically, for example by injection molding, melt casting, pressing, kneading or extrusion, if desired with a subsequent calendering step.
After film formation, volatile components such as solvents or plasticizers can be removed.
If crosslinking of the layers is desired, this can be carried out in a manner known per se, for example by irradiation with ionic or ionizing radiation, an electron beam, preferably at an acceleration voltage of from 20 to 2000 kV and a radiation dose of from 5 to 50 Mrad, UV or visible light, where, in a customary manner, an initiator such as benzil dimethyl ketal or 1,3,5-trimethylbenzoyl-triphenylphosphine oxide can be advantageously added in amounts of, in particular, at most 1% by weight based on the constituents to be crosslinked in the starting materials and the crosslinking can advantageously be carried out over a period of, in general, from 0.5 to 15 minutes, advantageously under inert gas such as nitrogen or argon; by thermal free-radical polymerization, preferably at above 60xe2x96xa1 C., where an initiator such as azobisisobutyronitrile can advantageously be added in amounts of, in general, at most 5% by weight, preferably from 0.05 to 1% by weight, based on the constituents to be crosslinked in the starting materials; by electrochemically induced polymerization; or by ionic polymerization, for example by acid-catalyzed cationic polymerization, where suitable catalysts are, first and foremost, acids, preferably Lewis acids such as BF3 or, in particular, LiBF4 or LiPF6. Catalysts containing lithium ions, for example LiBF4 or LiPF6, can advantageously remain in the solid electrolyte or separator as conducting salt.
The layers described herein can also comprise a dissociable compound containing lithium cations, viz. a conducting salt, and, if desired, further additives such as, in particular, organic solvents, viz. an electrolyte.
Some or all of these materials can be added to the mixture during the production of the layer or can be introduced into the layer after production of the latter.
Conducting salts which can be used are the generally known conducting salts which are described, for example, in EP-A 0 096 629. According to the present invention, the conducting salt used is preferably LiPF6, LiBF4, LiClO4, LiAsF6, LiCF3SO3, LiC(CF3SO2)3, LiN(CF3SO2)2, LiN(SO2CnF2n+1)2, LiC[(CnF2n+1)SO2]3, Li(CnF2n+1)SO3, where n is in each case from 2 to 20, LiN(SO2F)2, LiAlCl4, LiSiF6, LiSbF6 or a mixture of two or more thereof, with particular preference being given to using LiBF4 or LiPF6 as conducting salt.
These conducting salts are used in amounts of from 0.1 to 50% by weight, preferably from 0.1 to 20% by weight, in particular from 1 to 10% by weight, in each case based on the material forming the respective layer.
The layers forming the composite of the present invention generally have a thickness of from 5 to 500 xcexcm, preferably from 10 to 500 xcexcm, more preferably from 10 to 200 xcexcm. The composite, which can have, for example, the form of a film, a cuboid, a cylinder, a zig-zag roll or a flat roll (e.g. with oval side faces), generally has a total thickness of from 100 xcexcm to a few cm.
Furthermore, the present invention also provides a process for producing a composite according to the invention, which comprises joining the separator layer or layers Aa/Ab, the cathode layer or layers B, the anode layer or layers C and, if present, the bonding layer or layers D to one another by lamination by means of pressure and/or temperature. It should be ensured that, depending on the material used for the bonding layer, joining can always be carried out at room temperature or at temperatures up to 50xe2x96xa1 C. or by hot lamination.
In the hot or cold lamination, all customary techniques such as roller melt methods, simple pressing and extrusion lamination can be employed.
In the case of hot lamination, the temperatures used are generally from about 50xe2x96xa1 C. to about 250xe2x96xa1 C., preferably from about 700xe2x96xa1 C. to about 200xe2x96xa1 C. and more preferably from about 100xe2x96xa1 C. to about 180xe2x96xa1 C.
In detail, the following procedure may be employed:
Firstly, a bonding layer D is applied, for example, to a temporary support film, as defined above, which can later be removed or drawn off. The support film can also be one which does not have to be removed. Particular mention should be made of films of one of the above-defined conventional separators which either become ion-conducting as a result of swelling or are intrinsically ion-conductive or else contain micropores, e.g. the likewise above-defined microporous PE films, open-celled foam films, nonwovens and woven fabrics.
This first composite is subsequently transferred, e.g. by means of heat and/or pressure, to a cathode or anode layer B/C or a separator layer Aa/Ab. This gives a laminated composite which can be laminated with further layers as defined herein.
This procedure can be repeated as many times as necessary to obtain the desired composite of the present invention. In this way, it is possible to obtain a composite which comprises a cathode, an anode and a separator and can thus be transferred directly into a battery housing. For this purpose, the stack or roll obtained after the abovementioned shaping steps is bonded by action of heat and pressure, giving a firmly welded electrode stack or roll. The heat required for this can be generated, inter alia, by thermal radiation, ultrasound, friction, microwave energy. This stack or roll can then be introduced into a battery housing. If, in the production of the stack or roll, two electrode films coated on one side meet and as a result, for example, two terminal lead metals lie on top of one another, another bonding layer D can be introduced between these two films in order to produce a non-positive connection between these two layers as well.

Composite body suitable for utilization as a lithium ion battery

Abstract: A composite comprising:

Abstract: A) at least one separator layer Aa which comprises a mixture Ia, comprising a mix IIa consisting of:

Abstract: (a) from 1 to 95% by weight of a solid III having a primary particle size of from 5 nm to 20 xcexcm; and

Abstract: (b) from 5 to 99% by weight of a polymeric composition IV;

Abstract: B) at least one cathode layer B which comprises an electron-conducting, electrochemically active compound which is able to release lithium ions on charging, and


An electrical assembly including a substantially planar substrate having at least one recess therein and a plurality of electrical components. The electrical components are positioned in the at least one recess and include a first electrical component and a second electrical component. Each of the electrical components has a body and an electrical connection. The electrical connection of the first electrical component and the electrical connection of the second electrical component are aligned with each other when the body of the first electrical component is in a recess and the body of the second electrical component is in a recess.

It is known in the art to print thick film conductive inks on a substrate and cure the inks to produce an electrical circuit assembly. Various resistivities of the conductive ink are used and additional electrical components may be attached to the substrate to manufacture the electrical circuit. Polymer thick film circuits may be manufactured using a polyester dielectric substrate and screen printed thick film conductive inks. High speed screen printing techniques can be used, and multi-layer circuits may be manufactured utilizing dielectric materials as insulating layers. Both active and passive surface mount components can be added to the substrate. The substrate with the mounted components can be encapsulated to shield the assembly from the effects of moisture.
Alumina (Al2O3) is often utilized as a ceramic substrate for the printing of thick film circuits thereon. Passive and active components can be mounted to conductive pads screen printed on the substrate. The alumina substrate is typically a planar rectangular shaped substrate. Alumina is a widely used material due to availability, relatively low cost and stable physical properties. It is relatively easy to fabricate and retains its strength at high temperatures.
Alumina can be manufactured in thicknesses from 0.5 mm up to 12.5 mm. The power density in watts/cm2 for alumina is approximately 23.25 W/cm2. Alumina also has a relatively high dielectric strength of 2.39×105 V/in and an electrical resistivity of 3.28×1013 Ohms ft.
It is known to encapsulate or contain high voltage circuits in an enclosure filled with oil having a high dielectric and breakdown characteristic, to allow the proximity of high voltage components in the assembly. High voltage circuits can be pre-positioned by way of a printed circuit board or point-to-point wiring, and the completed assembly encapsulated to allow safe installation into another assembly.
Current known methods of assembling electrical circuit components involve the connection of leads of the electrical component to an intermediate structure, such as a solder post or a solder pad of a printed circuit board. The lead of the electrical component typically is formed so that it can be inserted into a hole in the printed circuit board, and the lead then soldered to a pre-tinned pad on the circuit board. If the lead is to be connected to a solder post, the lead is bent around the post and then soldered thereto. Solder posts typically have leads of other components or wires soldered thereto.
Although rarely known to be done in production electrical assemblies, leads of electrical components can be directly soldered together without the support of a solder post or a printed circuit board. Typically the leads are twisted together by hand, and solder is applied to the twisted leads to ensure the electrical connection.
Leadless electrical components are placed on surface mount circuit boards and are held in place with a small amount of adhesive. The ends of the leadless components are then soldered to pads on the circuit board, which provides mechanical support and electrical connections for the leadless component.
Each of the known methods described above requires a mechanical attachment of either the leads or the component prior to soldering.
What is needed in the art is an assembly method that results in pre-positioned electrical components without the use of an attachment procedure.


A method for designing an arrayed waveguide grating that includes input and output couplers, input and output slabs, and a plurality of arms connecting the input and output slabs includes steps of determining a desired amplitude response for the arrayed waveguide grating. A desired dispersion response for the arrayed waveguide grating is determined. Input and output couplers are designed to produce the desired amplitude response. The lengths of the arms of the arrayed waveguide grating are perturbed to produce a flat or linear dispersion. In addition, the polarity of a group delay, dispersion and dispersion slope response of an arrayed waveguide grating can also be changed by adjusting Individual lengths of the waveguide arms. The group delay, dispersion and dispersion slope of a multiplexer and a demultiplexer can be matched to substantially cancel.

The present invention relates to arrayed waveguide gratings, and more particularly to systems and methods for controlling both the dispersion and passband characteristics of arrayed waveguide gratings.
Dispersion of a material relates to the speed that energy at different wavelengths travels through a material. Controlling the dispersion of arrayed waveguide gratings (AWGs) will be essential in 40 Gigabit per second (Gbps) transmission systems and in spectrally efficient 10 Gbps systems (50 GHz spacing). Having the ability to design the dispersion characteristics in an AWG offers significant advantages.
AWGs typically include an input waveguide, a slab free-propagation region, an arrayed waveguide grating, a slab-focusing region and output waveguides. Conventional AWG designs have obtained a flattened AWG intensity passband by applying a multi-modal structure (MMI, parabolic horn, etc . . . ) to the standard AWG design at the entrance of one slab and a standard taper on the other slab. Because the passband is the result of the convolution between the two modes, the spectrum gets flattened. However, this design method leads to high dispersion and dispersion slope in the passband due to the non-flat phase of the multi-modal structure.
A second approach modifies the arrayed waveguide gratings to generate a sinc-like distribution that leads to a dispersion-free flattened passband. This approach uses a standard input/output in the slabs but modifies the amplitude distribution by adding some loss on some waveguides (amplitude) and changing the length of some waveguides (phase).
In U.S. Pat. No. 6,195,482 to Dragone, which is hereby incorporated by reference, the design of an arrayed waveguide grating is optimized by adjusting arm lengths and utilizing multi-mode input and output couplers to produce a specified passband behavior. Control of dispersion of AWGs is not discussed.
A method according to the invention for designing an arrayed waveguide grating that includes input and output couplers, input and output slabs, and a plurality of arms connecting the input and output slabs includes the step of determining a desired amplitude response for the arrayed waveguide grating. A desired dispersion response for the arrayed waveguide grating is determined. Input and output couplers are designed to produce the desired amplitude response. The lengths of the arms of the arrayed waveguide grating are perturbed to produce a flat or linear dispersion.
In another aspect of the invention, an arrayed waveguide grating includes input and output couplers, input and output slabs, and a plurality of arms connecting the input and output slabs. The input and output couplers produce a desired amplitude response for the arrayed waveguide grating. A length of the arms is adjusted to produce a flat or linear dispersion.
In yet another aspect of the invention, an arrayed waveguide grating includes a parabolic input coupler, a parabolic output coupler and an input slab connected to the parabolic input coupler. An output slab is connected to the parabolic output coupler. A plurality of arms connect the input and output slabs. The parabolic input and output couplers produce a flat passband response. Individual lengths of the arms are adjusted to produce a flat dispersion response.
In still another aspect of the invention, a method for changing the sign of a linear dispersion response of an arrayed waveguide grating includes the steps of connecting an input coupler to an input slab. An output coupler is connected to an output slab. The input and output slabs are connected using a plurality of waveguide arms. Individual lengths of the waveguide arms are adjusted to reverse the sign of a group delay, dispersion and dispersion slope of the arrayed waveguide grating.
In yet another aspect of the invention, an optical system includes a multiplexer that multiplexes a plurality of optical signals that are input to the multiplexer and outputs a multiplexed optical signal. The multiplexer has a first group delay, a first dispersion and a first dispersion slope. The first group delay, the first dispersion and the first dispersion slope have one of a positive and negative polarity. A demultiplexer demultiplexes the multiplexed optical signal that is input to the demultiplexer and outputs the plurality of optical signals. The demultiplexer has a second group delay, a second dispersion and a second dispersion slope. The second group delay, the second dispersion and the second dispersion slope have the other of a positive and negative polarity. The first and second group delay, dispersion and dispersion slope substantially cancel.
Further areas of applicability of the present invention will become apparent from the detailed description provided hereinafter. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention.

Controlling the dispersion and passband characteristics of an arrayed waveguide grating


Related ingredient names are extracted from ingredient names included in recipes while reducing the time and effort of a person. An information processing apparatus acquires one or more ingredient names included in each of one or more recipes included in one division of a plurality of divisions of recipes. Next, on the basis of an ordinal number of presentation of each of the acquired ingredient names in an ingredient list in the recipe, the information processing apparatus calculates a value indicating a probability that the ingredient name is a name of a main ingredient of the recipe belonging to the one division for each of the ingredient names. Then, the information processing apparatus associates a plurality of the ingredient names, among the acquired ingredient names, whose calculated values satisfy a predetermined condition with each other as related terms and stores the plurality of the ingredient names in a storage means.

Conventionally, a system is known which searches for recipes posted from users by using a specified search condition and presents the recipes. This system enables a user who posts a recipe to input, for example, ingredient names as information indicating ingredients used for cooking. The system searches for, for example, a recipe in which an ingredient indicated by an ingredient name specified as the search condition is used for cooking.
Patent Document 1 discloses a technique of storing an attribute value of each ingredient used in a recipe for each recipe, determining a similarity between a pattern of an attribute value of an ingredient for which a substitute ingredient should be presented and a pattern of an attribute value of another ingredient, and presenting an ingredient, as a substitute means, which has an attribute value of a pattern substantially similar to the pattern of the attribute value of the ingredient for which a substitute ingredient should be presented.

Information processing apparatus, information processing method, and information processing program