公开(公告)号：US4707911A

公开(公告)日：1987-11-24

申请号：US3090

申请日：1987-01-14

申请人： Frederick P. Kober ,  Oscar V. Montefusco

发明人： Frederick P. Kober ,  Oscar V. Montefusco

IPC分类号： H01M4/00 ,  H01M4/18

CPC分类号： H01M4/18 ,  H01M4/00 ,  Y10T29/49115

摘要： Porous electrodes are provided for lead-acid storage batteries without supporting plates or grids. The electrodes are porous, self-supporting, structurally integral and electrically continuous. Lead-acid batteries incorporating such electrodes exhibit improved performance characteristics as compared to conventional lead-acid batteries. The electrodes are made by forming a molten mixture of a metal (e.g. lead) and a pore forming component (e.g. cadmium), cooling and forming the molten mixture into a solid electrode with the pore forming component distributed therethrough, removing the pore forming component from the solid electrode to leave a network of voids defining the pores, and oxidizing the metallic walls within the pores to form a coating of electrochemically active material (e.g., lead dioxide) on the walls within the pores.

摘要翻译： 为无酸性蓄电池提供多孔电极，无需支撑板或网格。 电极是多孔的，自支撑的，结构上整体的和电连续的。 与常规铅酸电池相比，包含这种电极的铅酸电池具有改进的性能特征。 电极通过形成金属（例如铅）和成孔组分（例如镉）的熔融混合物而制成，将熔融混合物冷却并形成固体电极，其中孔形成组分分布在其中，从孔中除去成孔组分 固体电极留下限定孔的空隙网络，以及氧化孔内的金属壁，以在孔内的壁上形成电化学活性材料（例如二氧化铅）的涂层。

公开(公告)号：US4098258A

公开(公告)日：1978-07-04

申请号：US743438

申请日：1976-11-19

申请人： Frederick P. Kober

发明人： Frederick P. Kober

IPC分类号： F24V30/00 ,  H05B3/10 ,  F24J1/00 ,  H01M2/24

CPC分类号： H05B3/10

摘要： A complex electrochemical heat-generating element characterized by a two-surfaced anode layer, two separator layers of porous, absorbent material, one on either surface of the anode layer, two cathode layers, one in contact with each of the separator layers, and electrically conductive connectors extending through the cathode layers, separator layers and anode layer to conduct an electric heating current between the anode and cathode layers. Preferred embodiments relate to specific arrangements of connectors.

摘要翻译： 一种复杂的电化学发热元件，其特征在于两面阳极层，多孔吸收材料的两个分隔层，阳极层的任一表面上的一个，两个阴极层，一个与每个隔离层接触，以及电 导电连接器延伸穿过阴极层，隔离层和阳极层，以在阳极层和阴极层之间传导电加热电流。 优选实施例涉及连接器的具体布置。

公开(公告)号：US4095583A

公开(公告)日：1978-06-20

申请号：US743437

申请日：1976-11-19

申请人： Russell H. Petersen ,  Edmund A. Weaver ,  Frederick P. Kober

发明人： Russell H. Petersen ,  Edmund A. Weaver ,  Frederick P. Kober

IPC分类号： H01M6/36 ,  A61F7/00 ,  A61F7/02 ,  A61F7/03 ,  A61F7/08 ,  F24J1/00 ,  F24J3/00 ,  H01M6/32 ,  H05B3/10 ,  F24J1/04

CPC分类号： A61F7/03 ,  A61F2007/0276

摘要： A self-contained warming pad characterized by a heating element, an adjacent dose of activating liquid within a frangible container, and a substantially liquid-impervious cover enclosing the element and frangible container and having at least one tortuous air passage therethrough. Features include a cover having thermal insulating qualities, and a frangible container made of a meltable substance having a melting point chosen to control the upper temperatures of the pad. Other features relate to a cover configuration which provides an annular breathing passage, and a porous resilient mass within the pad which provides a substantial breathing capacity. The heating element is preferably an electrochemical element, and most preferably a complex electrochemical element having two cathode layers and one anode layer in a sandwich-like structure.

摘要翻译： 一种独立的加热垫，其特征在于加热元件，在易碎容器内的相邻剂量的活化液体，以及基本上液体不可渗透的盖，其封闭元件和易碎容器并且具有穿过其中的至少一个曲折的空气通道。 特征包括具有绝热特性的盖，以及由可熔物质制成的易碎容器，所述易熔物质具有被选择用于控制焊盘上部温度的熔点。 其它特征涉及提供环形呼吸通道的盖构造，以及衬垫内的多孔弹性块，其提供了大量的呼吸能力。 加热元件优选为电化学元件，最优选为具有夹层状结构的两个阴极层和一个阳极层的复合电化学元件。

公开(公告)号：US4094298A

公开(公告)日：1978-06-13

申请号：US743187

申请日：1976-11-19

申请人： Frederick P. Kober

发明人： Frederick P. Kober

IPC分类号： B01J19/00 ,  F24V30/00 ,  H05B3/06 ,  H05B3/10 ,  F24J1/04

CPC分类号： H05B3/06 ,  H05B3/10

摘要： An improvement in the separator layer of an electrochemical heating element having two electrode layers, a separator layer of porous, absorbent material therebetween, and electrically conductive connector means extending through the electrode and separator layers. The improved device includes structural spacing means interposed between one of the electrode layers and at least a portion of the other electrode layer to limit compression of the separator layer material. In one embodiment, discrete mechanical spacers are placed immediately adjacent to the connector means. In another embodiment, a recessed surface portion is formed in one of the electrode layers and the adjacent separator layer has a mating portion on one side which is received into the recessed surface portion.BACKGROUND OF THE INVENTIONThis invention relates to electrochemical heat-generating elements, and, in particular, to improvements in uniformity and performance reproducibility in such elements.The prior art as taught by Kober in U.S. Pat. No. 3,774,589 described an electrochemical heater element having an anode layer and a cathode layer and a suitable porous, highly absorbent separator means situated therebetween, the electrode layers being connected one to another internally by electrically conductive short-circuiting members, such as staples and the like. Introduction of a suitable electrolyte into this construction initiates an electrochemical heat-producing reaction.It has been shown on theoretical grounds that this heater construction results in efficiencies of energy conversion, (that is, the conversion of the chemical energy inherent in the electrochemically active materials to thermal energy) approaching 100%. However, in practice, although the energy conversion reaction proceeds at an efficiency approaching 100%, reproducibility in the total heat output and output pattern is well below acceptable levels unless extreme care is taken during the manufacturing of these elements. Such extreme care and unreasonably close tolerances during manufacture are both time-consuming and costly. This problem applies to heating elements of the type disclosed in U.S. Pat. No. 3,774,589, and a new heat generating element which is disclosed in a concurrently filed, co-pending patent application of Frederick P. Kober entitled COMPLEX ELECTROCHEMICAL HEATING ELEMENT.Experimentation has shown that this less than acceptable level of reproducibility can be attributed to a non-reproducible compression of the absorbent separator material contained within the electrochemical heat producing element. Unless separator compression is eliminated or, at best, limited, the heat generating element absorbs varying quantities of activating fluid, that is, either water or an electrolyte solution, during activation. Furthermore, if the separator is compressed and held mechanically beyond a certain limit, the electrolyte which is absorbed is not able to distribute or wick uniformly throughout the heater structure. Hence, the heat generating reaction has a tendency to progress non-uniformly across the element with the result of less than maximum utilization of the available active materials.In short, this non-reproducible compression of the separator material occurring in normal assembly of the electrochemical elements results in a changing internal volume (from element to element) available for the absorption of electrolyte during activation. And, particularly if this separator compression is held beyond a certain limit, the absorbed electrolyte is not distributed uniformly throughout the heat-producing element.It has been demonstrated experimentally that, for simple electrochemical heating elements of the type disclosed in U.S. Pat. No. 3,774,589, using standardized anode layer, cathode layer and separator layer stock, and standard electrolyte concentrations, a minimum volume of electrolyte solution per square inch of heater element is required to insure efficient, reliable activation and to achieve maximum conversion of the active material to thermal energy. The minimum required volume of electrolyte has been determined to be on the order of 1.5cc per square inch of heater element for the standardized elements tested. Experience has shown, however, that, for a maximum rate of heat generation and maximum production of total heat, at least about 1.67cc of electrolyte solution per square inch of heater should be used. Substantial additional amounts of electrolyte solution above this minimum required volume do not significantly affect overall heater element performance. It has been found that an electrolyte volume in the range of about 1.67 to 2.4cc per square inch of heater element is effective. If an electrolyte volume much above about 2.4cc per square inch were used, the overall rate of heat generation would be diminished due to the larger mass of internal liquid to be heated.These minimum volumes of electrolyte are all above that required stoichiometrically to sustain the electrochemical heat-generating reaction. But such minimum volumes of electrolyte appear to be necessary: (1) to assure uniform wetting and distribution of the liquid throughout the heater structure, and (2) to provide sufficient electrolyte solution for the hydrolysis reaction(s) which accompany and probably compete with the electrochemical reaction. Regardless of the exact reasons, however, the heat-generating structure must be capable of absorbing at least a minimum required volume of electrolyte for it to function efficiently and reproducibly.In an attempt to improve the electrolyte capacity and increase the ease of reproducing performance characteristics of electrochemical heating elements of the type disclosed in U.S. Pat. No. 3,774,589, one might consider using a substantially thicker layer of separator material or a multi-layered separator. However the use of a thicker or multi-layered separator results in an increase in internal resistance of the heater element, causing a decrease in the rate of heat generation. Further, the use of a thicker or multi-layered separator does not substantially reduce or eliminate the problem of separator compression.Thus, there has been a need for an electrochemical heat-generating element having good reproducibility of performance and having substantial capacity for an electrolyte solution in its separator layer.BRIEF SUMMARY OF THE INVENTIONThe present invention is an improvement in electrochemical heat-generating elements of the type having at least two electrode layers, including an anode of electrochemically active, electrically conductive, oxidizable material and a cathode of electrochemically active, nonmetallic, reducible material, a separator layer of porous, absorbent material between the electrode layers, and electrically conductive connector means extending through the electrode and separator layers. The improvement relates to a structural spacing means interposed between one of the electrode layers and at least a portion of the other electrode layer whereby to limit compression of the separator layer.In one embodiment, the structural spacing means includes discrete mechanical spacers placed immediately adjacent to the connector means between the electrode layers. Also disclosed are variations of this embodiment. In another principal and highly preferred embodiment, the structural spacing means includes one of the electrode layers being formed to define a recessed surface portion and the adjacent separator layer having a mating (or "wick") portion formed on one side and received into the recessed surface portion of the electrode layer. Variations of this embodiment are also disclosed and claimed.A substantial improvement in reproducibility of performance characteristics and elimination of undue separator compression are obtained by using the aforementioned discrete mechanical spacers. Such spacers may take the form of small planar pads which are situated between the separator material and one or both of the electrodes and pierced through by the electrically conductive connector means such as staples. The area of such pads in comparison with the area of the heating element is negligible. However, the interposition of such pads within the heating element structure reduces the pressure of the electrode layers on nearly all of the surface of the separator layer by applying the pressure through the spacers. Other sorts of mechanical spacers, including small metal eyelets and a great variety of other configurations of metallic or electrically inert materials, can be used to advantage. By using such mechanical spacers, much of the separator compression is eliminated and the retained electrolyte volume can be controlled within much closer tolerances. In this way, heat output can be maximized with excellent reproducibility from heater to heater.While the use of such mechanical spacers has proven effective, there may be certain difficulties in properly and reproducibly placing such spacers. Accordingly, an important alternate embodiment of this invention is the inventive "recessed" structure described and claimed herein. In such embodiment, at least one of the electrode layers is formed to define a recessed surface portion which may be centrally located on the surface of such electrode layer. Such recessed surface is preferably formed in the cathode layer. The adjacent separator layer has an additional built-up portion, either added to or formed with the basic portion of the separator layer, which mates with the recessed surface portion of the electrode layer. The electrically conductive connector means, such as staples, extend through the heating element in surface areas away from the recessed and mating portions.By virtue of this configuration, the mating portion of the separator layer can function as a wick for the separator layer, assuring that sufficient electrolyte solution is available. The recessed portion and mating portion (or wick) may be in a variety of shapes and sizes. Preferably the wick is within the range of about one-eighth to one-half of the width of the heat-generating element and most preferably on the order of about one-third the width of the element. However, it may be appreciated that a variety of sizes and shapes are operable and in some cases a multiplicity of wicks and a multiplicity of recessed portions would be acceptable.As already indicated, it is preferred that the recessed surface portion be formed in the cathode layer. However, the anode layer may be used for this purpose as well, although the performance which has been achieved in such structures has not been as dramatic as that derived from the preferred arrangement. In simple electrochemical heating elements, having one anode layer, one cathode layer and a separator layer, both the anode and cathode can be formed with a recessed portion. However there appears to be little if any additional advantage achieved with such a configuration. In complex elements having two cathode layers, two separator layers, and a center anode layer in a sandwich-like structure, each cathode layer may be formed to have a recessed surface portion and the adjacent separator layers may be formed with appropriate mating portions to provide a wicking structure for each separator.The highly preferred embodiments having the wick structure provide excellent reproducibility in performance from element to element. Furthermore, cost advantages are realized in production since special manufacturing procedures and extremely close tolerances may be eliminated. Even if the basic separator material, around the mating or wick portion, becomes compressed during assembly, the uncompressed electrolyte resevoir provided by the wicking structure is available to absorb the necessary quantity of electrolyte and distribute such electrolyte uniformly throughout the heater.The benefits and advantages derived from this invention, and, in particular, from the most preferred embodiment including the wicking structure, are especially important for electrochemical heating elements requiring a high rate of heat generation, sustained heat output over an extended period of time (for example, 20 minutes or longer), uniform heat generation per unit area of heater element, and/or rapid reliable activation. Elements designed for such performance have a generally higher sensitivity to variations caused by normal manufacturing procedures.Comparative data illustrating the advantage of reproducibility provided by this invention will be given hereafter.OBJECTS OF THE INVENTIONOne object of this invention is to overcome the aforementioned problems and shortcomings in electrochemical heating elements of the prior art.Another object of this invention is to provide electrochemical heating elements which are substantially uniform in performance.Another object of this invention is to provide an electrochemical heating element which may be manufactured with normal manufacturing procedures without concern for extremely close tolerances.Yet another object of this invention is to provide an electrochemical heating element in which there is a high utilization of electrochemically active materials.These and other important objects of the invention will be apparent from the following description of preferred embodiments and the discussion relating thereto.

摘要翻译： 具有两个电极层的电化学加热元件的隔离层的改进，其间具有多孔吸收材料的隔离层和延伸穿过电极和隔板层的导电连接器装置。 改进的装置包括插入在一个电极层和另一个电极层的至少一部分之间的结构间隔装置，以限制隔板层材料的压缩。 在一个实施例中，离散的机械间隔件紧邻于连接器装置放置。 在另一个实施例中，在一个电极层中形成凹面部分，并且相邻的隔离层在一侧上具有接合到凹入表面部分中的配合部分。