WO2019083382A2

WO2019083382A2 - A composite lead-acid battery comprising current collectors based on shaped elements made of conductive porous carbon and processes for manufacturing

Info

Publication number: WO2019083382A2
Application number: PCT/PL2018/000100
Authority: WO
Inventors: Andrzej CZERWIŃSKI; Piotr Podsadni; Zbigniew Rogulski; Michał Bystrzejewski; Jakub LACH; Kamil Wróbel
Original assignee: Czerwinski Andrzej; Piotr Podsadni; Zbigniew Rogulski; Bystrzejewski Michal; Lach Jakub; Wrobel Kamil
Priority date: 2017-10-24
Filing date: 2018-10-24
Publication date: 2019-05-02
Also published as: EP3701578A2; WO2019083382A3

Abstract

The present invention discloses components of a CLAB-type composite lead-acid battery and a CLAB-type composite lead- acid battery having lightweight composite current collectors having non-lead substrates made of conductive porous carbon produced in the form of shaped elements with a specific desired target geometry, porosity and surface architecture. Current collectors have increased mechanical strength, increased electrical conductivity, increased ability to use the active mass filling the collector, and minimized the amount of lead used for their construction. The carbon substrates of current collectors can be produced in any shape, thanks to which it is possible to produce current collectors and CLAB-type batteries of any shape. By using the solution according to the present invention, vehicle designers or other devices requiring the use of a starter battery or an electrochemical energy source will not be limited by the need to use a standard, cuboidal battery chamber. A method for manufacturing of shaped elements made of conductive porous carbon, using the process of carbonization of polymeric materials, consisting of heating in a gaseous environment a polymeric material impregnated with a suitable resin or a mixture of resins, that undergoes thermal hardening followed by carbonization in an anaerobic or reducing atmosphere, according to the present invention is characterized in that a porous polymeric material is subjected to mechanical pre-treatment to obtain shaped elements made of a porous polymeric material having the desired geometry, taking into account the expected dimensional changes during the carbonization process, which are then impregnated with a resin or a mixture of resins, then the impregnated shaped elements are optionally subjected to further mechanical machining, and then the shaped elements are hardened, then embedded in the holder, the whole is placed in the carbonization chamber and carbonized, which results in formation of shaped elements made of conductive porous carbon of a desired, target geometry without the need for their further mechanical machining. A method for manufacturing of current collectors of a composite lead-acid battery, the collector having a substrate made of porous non-lead conductive material, coated at least partially with lead or lead alloy and having an electrical contact, according to the present invention is characterized in that the substrate made of porous non-lead conductive material used has increased mechanical strength, and was subsequently made in a form of shaped elements with a specific desired target geometry, dimensions, shape, spatial architecture, relief and porosity, in a way that does not require mechanical machining of the conductive material from which the substrate is made of. A method for introducing an active mass into the current collector of a positive or a negative electrode of lead-acid battery, which collector is equipped with an electrical contact made of lead or lead alloy, employing a form with an inner shape and depth identical with the target shape of said electrodes, which form is made of a material resistant to sulfuric(VI) acid, preferably of PTFE, characterized in that the active mass is introduced by gravitational shaking, and an excess of the paste located above the upper edge of the form is collected by means of a doctor blade; A lead-acid composite battery having at least one cell comprising at least one positive electrode, at least one negative electrode, electrolyte and means ensuring current flow, at least one electrode having a current collector made of porous non- lead substrate covered at least partially with a surface layer of lead or its alloy, and filled with an appropriate active, cathodic or anodic active mass, characterized in that the current collectors of the electrodes have substrates made of porous non-lead conductive material of increased mechanical strength, previously made in the form of shaped elements with a specific desired target geometry, dimensions, shape, spatial architecture, relief and porosity, in a way that does not require mechanical machining of the conductive material from which the substrate is made of.

Description

A COMPOSITE LEAD-ACID BATTERY COMPRISING CURRENT COLLECTORS BASED ON SHAPED ELEMENTS MADE OF CONDUCTIVE POROUS CARBON AND PROCESSES FOR MANUFACTURING

The present invention relates to a composite lead-acid battery comprising current collectors based on shaped elements made of conductive porous carbon and processes for manufacturing thereof. The invention discloses a method for manufacturing of shaped elements made of conductive porous carbon, a method for manufacturing of current collectors, a method for introducing an active mass into the current collector of the lead-acid battery electrode, and the composite lead-acid battery comprising the composite current collectors of increased mechanical strength and increased electrical conductivity, based on shaped elements of a desired geometry and made of conductive porous carbon.

The lead-acid battery was invented in 1859 by Gaston Plante, a French physicist, and until now it is one of the most commonly used electrochemical power sources. The lead-acid battery enables reversible storage of electricity in a reliable and extremely cheap manner in comparison to other currently known types of electric batteries. Due to the heavy weight of lead elements, lead-acid batteries are used only in devices for which a relatively high total weight is not a significant problem, in such devices as starting batteries in vehicles powered by combustion engines. Lead-acid batteries with a special design are taken into consideration as power sources for cars with hybrid and electric drive.

The current collectors of positive and negative electrodes in lead-acid battery are in form of grids, trusses or openwork structures having an active surface made of lead or lead alloy. The active mass, appropriately selected for the type of electrode (negative or positive) fills the holes of the current collector. The current collector on the surface of contact with active mass must be resistant to concentrated sulfuric acid and active mass components, such as lead, lead oxide (IV) and additives. To meet these requirements, current collectors of electrodes having lead or lead alloy surface are used. In the case of traditional collectors, solid lead structures are used. In batteries, the electrodes are grouped in the so-called cells rendering a voltage of 2 V, containing at least one positive electrode and at least one negative electrode. The cells and flooded with 40% sulfuric acid and connected in series to provide voltage of 12 V.

To raise a relatively low specific energy and capacity of the lead-acid batteries, standard solid lead grids are replaced with lighter matrices of lighter materials, e.g. polymer grids [J. Power Sources, 46 (1993) 171], ceramic grids [US5126218], graphite grids [J. Power Sources, 161 (2006) 1392] or reticulated glassy (vitreous) carbon gratings [PL167796 Bl]. The matrices are coated with a surface layer of lead or lead alloy.

In recent years, a new type of lead-acid battery has been developed, which has carbon-lead current collectors covered with a thin lead layer. The carbon-lead collectors are much lighter than the commonly used current collectors made of solid lead. Due to the use of lower-mass current collectors, it was possible to construct a CLAB-type (Carbon Lead Acid Battery) composite lead- acid-carbon battery, with significantly increased specific capacity compared to traditional lead- acid batteries (PL180939, PL211599, PL211918, US2005 / 0100791 Al , US2006 / 0292448 Al, WO03 / 028130 Al, WO2006 / 092060 Al).

Current collector substrates in composite lead-acid batteries are formed from conductive porous carbon (CPC) - also known as reticulated vitreous carbon (RVC) by cutting blocks of such material. During the cutting process, however, the material undergoes partial crumbling at the edges, and microcracks appear in its structure. Further modifications of the spatial architecture or boring the relief on the surfaces of the carbon element result in further material losses and additionally weakens its structure. In addition, microcracks and crumbling of the material reduce its conductivity and the ability to make use of the active mass filling the collector.

Conductive porous carbon has been produced for over 30 years. This material is obtained in result of slow carbonation of polymeric foams saturated with suitable curable resins or their precursors. The obtained carbonisate, formed as a result of carbonization of polymers saturated with these resins, has a spatial structure of polymer foam and electrical properties of so-called glassy carbon. The carbonization of monolithic shaped elements (bodies) made of hardened resins leads to the formation of monolithic blocks of glassy carbon.

Methods for obtaining monolithic blocks of glassy carbon and conductive porous carbon by carbonization of the cured phenol-formaldehyde resin are known [GB956452, PL130425, PL137061, PL166256].

Methods for obtaining a conductive porous carbon are known. Patent PL156386 describes the production of porous glassy carbon from a phenol-formaldehyde resin and methanol and makes it possible to obtain a product with a porosity of 0.5-1.2%. The US3927186 discloses the production of porous vitreous carbon having a porosity of 96.5-98.5% from reticulated polyurethane foams supersaturated with furan or furfuryl resins or immersed in resins precursors that polymerized in situ during impregnation. The US4024226 describes a process for the formation of glassy porous carbon from reticulated polyurethane foams supersaturated with phenol-resol, epoxy or polymethylsiloxane resin. The US4067956 discloses the preparation of anisotropic porous glassy carbon from reticulated polyurethane foams supersaturated with phenol-formaldehyde resin and furfuryl alcohol which was polymerized in situ during the supersaturation process. In turn, US4022875 describes the preparation of a porous glassy carbon from a polyurethane foam supersaturated with a furfuryl alcohol polymerizing in situ to form a furfuryl resin. Patent BR102012008326 describes a method for the production of glassy coal and carbonaceous coatings from a partially carbonised furfuryl resin. The patent US6245313 describes a multi-step method for the formation of glassy carbon materials, in which the machining of the carbon material during the preparation is foreseen. US8052903 describes a method for the pyrolytic generation of conductive carbon from fiber materials having a spatial structure impregnated with polymer resins.

Polish patent application No. P.419946 describes a method for the carbonization of polymeric materials that enables the carbonization process to be carried out in atmospheric air or in a protective atmosphere. The method envisages the carbonization of the polymeric material in the closed carbonization chamber after its tight covering with a protective powder of carbon- rich material. The material effectively captures oxygen from the atmosphere present in the carbonization chamber, protecting the carbonisate from oxidation, while itself undergoing oxidizing with the loss of mass.

The above solutions allow obtaining conductive coal in solid or porous form, however, they do not describe the possibility of controlling the geometry and porosity of the target product. Based on the solutions presented so far, the control of the geometry of the conductive porous carbon can only be achieved by mechanical machining requiring the use of force, leading to material crumbling and to forming microcracks in its structure. Crumbling of the material on the cut surfaces causes losses and makes it impossible to obtain shaped elements of precisely defined dimensions. The presence of microcracks in the structure of conductive porous carbon strongly affects its mechanical and electrical properties. It is also common that carbon elements break during their mechanical treatment, which adds to material losses. Mechanical treatment also does not solve the problem of controlling the porosity reached in the carbonization process.

Current collectors of the positive and negative lead-acid battery electrodes have openwork structures. Collector openings are filled with an active mass, appropriately selected for the type of electrode - negative or positive. The current collector on the contact surface with active mass must be resistant to concentrated sulfuric acid and active compound components, e.g. lead, lead oxide (IV) and additives. Due to these requirements, current collectors of electrodes having a surface of lead or lead alloy are used. In the case of traditional collectors, solid lead structures are used, and in the case of CLAB-type batteries, the open-work carbon structure of the collector's substrate is covered with a protective layer of lead or its alloy. Lead and tin alloys are most commonly used.

The current collector substrate for the CLAB-type batteries are formed of conductive porous carbon by cutting blocks of this material. During the cutting process, however, the material undergoes partial crumbling at the edges, and microcracks appear in its structure. Further modifications of the spatial architecture or boring the relief on the surfaces of the carbon shaped substrate result in further material losses and additional weakening of its structure. In addition, microcracks and crumbling of the material reduce its conductivity and thus also the ability to make the full use of the active mass filling the collector.

Until now, to the substrate made of conductive porous carbon an electrical contact (outlet) in the form of the so-called "strap" is attached, and then the surface of the properly shaped substrate, optionally with the strap, is covered - in part or totally, with a thin layer of lead or lead alloy. The thickness of the lead layer usually varies between 10 and 200 μιη, depending on the type of electrode in which the collector is to be used. Negative electrodes usually have a thinner lead layer deposited on the carbon substrate, thus allowing for an additional reduction of the weight of the entire system. Lead or lead alloys are used to make lead coatings, most commonly lead and tin alloys are used. Various methods are known for providing electrical outlet from current collectors. An electrical outlet consisting of metallic lead strips threaded through the holes in the matrix of conductive porous carbon and tied-up together into a single wire [PL211918], but this solution is cumbersome because the carbon matrices often crumble when the lead strips are pushed therethrough. A similar construction is also known from patent PL211599.

A current collector in the form of a metal frame with a rectangular tip embedded in the outer edge of a porous carbon collector previously covered with metal or a metal alloy is known from publication US 2006/0292448 Al]. The use of a thick solid lead frame, however, increases the mass of the entire collector. In addition, this solution causes a significant increase in the thickness of the entire collector, because its thickness is the sum of the thickness of the carbon shaped element and the lead grate, which generates problems related to the optimization of the packing of the electrodes inside the battery housing. Also known is a current collector of the lead- acid battery electrode having a substrate of conductive porous carbon coated at least partially with a lead layer or its alloy with tin [Polish application P.408085]. The collector has an electrical outlet in the form of a cast located deep in the substrate, connected to a strap on one of its edges. The cast is casted by gravity and then rapidly cooled in the air stream. This type of electric outlet involves the use a relatively large amount of solid lead, which adversely increases the weight of the battery and reduces its specific capacity, simultaneously preventing the use of full potential of lightweighted composite lead carbon matrixes.

There is known a method of depositing metal layers on conductive substrates. There is also known a method of modifying the surface of a conductive porous carbon by depositing a lead galvanic coating [Polish applications P.392619, P.408085] and a copper galvanic coating [Polish application P.416941]. There is also known a method for the electroless deposition of surface metal layers (e.g. layers of: Pt-Rh-Ru, Pt-Sn, Pt-Ru, Pt-Rh, Ru-Rh, Rh-Sn, Ru-Sn) on a conductive substrate [patent PL207254] . There are known methods for depositing metal layers onto conductive substrates and non-conductive substrates by spraying/sputtering.

The prior art solutions do not allow for constructing a lead-acid-carbon battery that would fully benefit from the potential advantages related to using porous carbon-lead current collectors, and would minimize the weight of the battery. Current methods of obtaining current collector substrates provide shaped elements that are not free of microcracks and micro- damages, significantly reducing the conductivity of the current collector substrate and results in incomplete use of the active mass during battery operation.

Introducing the active mass into the current collectors of the lead-acid battery electrodes is a significant technological problem. Current collectors are in form of grids, trusses or openwork structures having a surface made of lead or lead alloy. In traditional batteries, grids are made of solid lead and in CLAB-type batteries the openwork carbon structure is covered with a layer of lead or its alloy. Irrespective of the type and design of the current collector, its openings are filled with active mass, appropriately selected for the type of electrode - negative or positive. The traditional system for pasting the current collectors comprise a feeder, pasting machine and a drying tunnel. In traditional systems, the pasting machine contains a system of stirrers and rollers, by means of which the active mass is mechanically pressed into the current collector holes in a continuous manner. On a properly constructed production line, it is possible to automatically paste up to 600 current collectors per minute. When pasting traditional current collectors, it is possible to apply a certain pressing force, because grids made of solid lead retain their shape under these conditions.

Composite carbon-lead current collectors having an openwork irregular structure are not resistant to pasting in traditional automatic pasting systems, because the rollers and agitators used therein may damage and destroy the collector structure. For this reason, pasting of collectors for CLAB-type batteries is carried out manually. In turn, the manual introduction of the active mass is slow and often leads to inaccurate and uneven pasting. This inaccuracy results mainly from the thickness of composite collectors, which is larger than the thickness of traditional solid lead collectors.

There is a known method for introducing the active mass into the current collector of the lead-acid battery electrode [Polish application P.409464] employing mechanical vibrations. For this purpose, a vibrating table containing a mold made of PTFE is used, in which the current collector is placed with a properly dosed portion of active mass on the top. After switching on the mechanical vibrations, the active mass penetrates spontaneously into the collector and the process takes 1-5 minutes. This method protects composite collectors against damaging, but is long-lasting, which is unfavorable for production line for manufacturing batteries.

The aim of the invention is to provide new components of the composite lead-acid battery and the process for manufacturing the same, allowing to fully exploit the potential advantages resulting from the use of carbon-lead collectors in the CLAB-type battery.

The essence of the invention

This and other objects of the present invention are achieved by providing a solution presented in the appended claims defining a process for manufacturing the conductive porous shaped elements (bodies) of a given shape and dimensions - claims 1-8, a process for manufacturing current collectors on a substrate in the form of shaped elements of the invention - claims 9-13 and a method for introducing an active mass into the current collector of the invention - claim 14, as well as a composite lead-acid battery - claim 15, wherein the at least one electrode has a current collector made by a process according to the invention using a substrate in the form of a conductive porous carbon shaped element of a given shape and dimensions and filled with the appropriate active mass: cathodic or anodic.

The present invention solves the problems known from the prior art related to the difficulties in mechanical processing of brittle conductive porous carbon shaped elements, the processing usually generating their crumbling and microcracks also adversely affecting the subsequent operation of the composite lead-acid battery. The present invention: - allows for manufacturing of conductive porous carbon shaped elements of increased mechanical strength, required porosity, geometry and surface architecture, without the need for mechanical processing of this brittle carbon material;

- allows for manufacturing of current collectors of electrodes, having a low weight, increased mechanical strength and increased ability to make use of an active mass filling the collector;

- allows for quick, efficient and effective introduction of an active mass into the composite current collector;

- provides a composite lead-acid battery of increased mechanical strength, increased electrical conductivity, increased ability to make use of the active mass filling the collector, reduced weight and minimized the amount of lead used in its construction.

The present invention is described in details in the following detailed description and in the working examples, with reference to the attached drawing, where:

Fig. 1 is a schematic diagram of a process for the production of shaped elements made of conductive porous carbon of a required geometry, dimensions, shape, spatial architectu re, relief and porosity, comprising individual process steps: cutting out a shaped element, impregnation, embedding in a holder, thermal curing and carbonization;

Fig. 2 schematical ly shows the experimentally determined mathematical relationship between the ratio of initial dimensions of a shaped element made of porous polymer material (XA, y_A, z_A) and the desired target dimensions a shaped element made of conductive porous carbon (xc, yc, zc) and impregnation time (H);

Fig. 3 schematically illustrates a process of mechanica l machining of shaped elements made of porous polymeric material comprising: cutting out shaped elements of a simple sha pe, cutting out shaped elements of a complicated shape, and cutting out and juxtaposing two shaped elements of different porosity;

Fig. 4 schematically shows a cross-section through :

- an empty carbonization holder consisting of a vessel having a base and side walls and of a lid, in a cross-section showing the inner space of the shape and dimensions corresponding to the target dimensions of the shaped element made of conductive porous carbon (top part of the figure), and the same holder in a cross-section with an impregnated shaped element made of porous polymeric material placed inside (bottom part of the figure);

- an empty holder in the form of a block with cut-outs corresponding to the target dimensions of a shaped element made of conductive porous carbon (top part of the figu re), and the same holder in a cross-section with impregnated shaped elements made of porous polymeric material placed in the cut-outs (bottom part of the figure);

- an empty holder for thin impregnated shaped elements made of a porous polymeric material, in the form of two flat blocks and thickness adjusters (top part of the figu re), and the same holder in a cross-section with a n impregnated thin shaped element made of porous polymeric material placed between the flat blocks (bottom part of the figure);

Fig. 5 schematically shows the hollow interior of the holder consisting of a vessel having a base, side walls and a lid, the shape and size of which correspond to the target dimensions of shaped elements made of conductive porous carbon: front view (left), side view (right);

Fig. 6 schematically shows a cross-section through a shaped element made of a porous polymeric material housed in a holder comprising a vessel having a base, side walls and a lid having additionally cut-outs, protrusions and wedges shaping the spatial architecture and relief of the shaped element made of conductive porous carbon (top part of the figure), and a shaped element made of conductive porous carbon with a relief and a channel extending through it (bottom part of the figure);

Fig. 7 schematically shows an impregnated shaped element made of porous polymeric material during carbonization, embedded in a holder tightly covered with a protective carbon-rich backfill powder material placed in a closed chamber furnace with a possible protective gas flow through the furnace;

Fig. 8 schematically depicts an impregnated shaped element made of a porous polymeric material during carbonization, embedded in a holder tightly covered with a protective carbon-rich backfill powder material placed in a retort with a cover that has a multi-point protective gas inlet in the bottom and a multi-point protective gas outlet in the lid, which retort is located in a closed chamber furnace with an optional protective gas flow through the furnace;

Fig. 9 is a graph showing:

A. experimental dependence of the ratio of the initial dimensions of a shaped element made of porous polymeric material to the final dimensions of a shaped element made of conductive porous carbon, as a function of impregnation degree, using a polyurethane foam curable with an ethanol solution of phenol-formaldehyde resin;

B. experimental dependence of the porosity of shaped elements made of conductive porous carbon, as a function of impregnation degree, using a polyurethane foam curable with an ethanol solution of phenol-formaldehyde resin;

C. experimental dependence of the impregnation time on impregnation degree using porous polyurethane foam curable with an ethanol solution of phenol-formaldehyde resin;

D. exemplary program of carbonization of polymeric material comprising a step of temperature rise in the range of 25-1050°C at a rate of 2.5°C/min, and an isothermal step at 1050°C for 60 minutes,

Fig. 10 is a schematic flow diagram of a process for manufacturing of porous current collectors of a required geometry, dimensions, shape, spatial architecture, relief and porosity, the process comprising the following individual process steps: preparation of a porous substrate with appropriate geometry, forming a relief and an architecture, hardening of the substrate; preparation of electrical contact, setting the substrate with additional elements such as grid, covering the substrate surface with a lead layer;

Fig. 11 schematically shows examples of an electric contact formation on porous substrates comprising a gravitational casting of the contact on the edge of the substrate and fixing of the strap, gravitational casting of the contact into the porous substrate, gravitational casting of the strap on the protrusion of the porous substrate;

Fig. 12 schematically illustrates a method of forming an electrical contact by means of a protrusion of the porous substrate, consisting of threading of a lead wire or a lead tape through a channel in the substrate at the base of the protrusion, fitting it into the relief of the protrusion and then gravitational casting of the strap on the porous substrate protrusion covering the lead wire or tape fitted into the relief of the protrusion;

Fig. 13 schematically shows exemplary shapes of current collectors that can be manufactured by the process according to the invention: a cuboidal collector with a strap for a lead-acid battery of a traditional shape, a cuboidal collector with a strap and a reinforcing frame for a lead-acid battery of a traditional shape, a circular and an annular collector for a lead- acid battery of a non-standard shape;

Fig. 14 illustrates a scheme of using the additional elements fitted into a relief of a substrate, for example: fitting in non-lead wires into a relief of a substrate prior to coating with lead, fitting in non-lead grids into a relief of a substrate prior to coating with lead, fitting in lead grids with a strap into a relief of a substrate after coating with lead;

Fig. 15 shows in a top view a porous current collector and a frame for use in gravitational shaking introduction of an active mass; and a scheme of the method of introducing the active mass into the porous current collectors by means of gravitational shaking using vertical mechanical vibrations;

Fig. 16 shows exemplary porous composite carbon-lead current collectors of a porosity of 20 ppi, with an electrical contact in a form of an edge casting with a strap, galvanically coated with a 10 μιη lead layer (left), and with a 100 μιτι lead and tin alloy layer having a tin content of 1.5% (right);

Fig. 17 shows pasted porous composite carbon-lead current collectors during seasoning: bright color collectors with Pb0₂ paste, darker collectors with Pb paste;

Fig. 18 shows packages of 2 V cells, formed by combining two positive electrodes and two negative electrodes with a use of a separator;

Fig. 19 shows a CLAB-type composite lead-acid battery with 2 V cells, prior to filling them with an electrolyte, closing and attaching the electrical contacts;

Fig. 20 is a graph comparing discharge characteristics of a CLAB-type battery in subsequent operation cycles with conventional lead-acid batteries (discharge current C/4, 1 h, charging for 2 h 55 min with a constant potential of 14.8 V at the maximum current C/2 and the next C/8 step, measurement at 25°C, the series of measurements was finished at a potential decrease below 10.5 V); Fig. 21 shows a graph of the capacity drop of a charged CLAB-type battery as a function of time (months) during its storage, with a trend line being marked.

Detailed description of the invention.

The present invention discloses a CLAB-type composite lead-acid battery having lightweight composite current collectors having non-lead substrates made of conductive porous carbon produced in the form of shaped elements with a required target geometry, porosity and surface architecture. Current collectors have increased mechanical strength, increased electrical conductivity, increased ability to make use of an active mass filling the collector, and minimized amount of lead used for their construction.

The carbon substrates of the current collectors can be manufactured in any shape, which makes possible to produce current collectors and CLAB-type batteries in any shape and application. Using the method according to the present invention, designers of vehicles and other devices requiring the use of a starter battery or an electrochemical power source will not be limited by the need to use a standard, cuboidal battery chamber. This is especially important when designing devices and vehicles of low weight, because it allows for distributing the battery weight evenly across the larger space of the vehicle. For example, it is possible to make a composite lead-acid battery of a shape that fills the frame of an electric bike or scooter. By adjusting the shape of the battery to the space requirements of the vehicle, its weight-balance will be advantageous in comparison to the vehicle using a conventional cuboidal battery placed in one part of it.

The method for manufacturing of shaped elements made of conductive porous carbon.

The present invention completely solves the problem of problematic mechanical machining of conductive porous carbon, because it allows formation of shaped elements made of this material with a required porosity and geometry, without the need for additional mechanical machining. The present invention allows the precise formation of shaped elements made of conductive porous carbon by appropriate mechanical machinig of the starting material (porous polymeric material or impregnated porous polymeric material) and its carbonization using a specially prepared holder.

According to the invention, the porous polymeric material is subjected to a mechanical pre- treatment consisting of cutting out a shaped element of an appropriate dimensions and geometry. Cutting the porous polymeric material is simple and does not require any use of specialized equipment, because the material has high flexibility, is easy to cut, and its cutting does not cause any crumbling, deformation or degradation of its structure. The shaped elements made of porous polymer material are then impregnated with a solution of thermosetting resin or a mixture of thermosetting resins, and then let to dry. During impregnation, the material expands, and its mass, volume and density increase. The impregnated shaped element made of porous polymeric material remain flexible and can be further shaped without damaging its structure. It is possible to prepare shaped elements made of porous polymeric material (impregnated or not) of any shape by machining a single block of a polymeric material. It is also possible to produce hybrid shaped elements by machining and juxtaposing two or more shaped elements made of polymeric material of the same or different porosity, which are joined together with use of the solution used for impregnation.

The impregnated shaped elements made of porous polymeric material are subjected to thermal hardening at a temperature of 70-180°C, preferably 120-160°C, followed by carbonization at a temperature above 200°C, preferably 200-1600°C, most preferably 700- 1100°C. In order to provide the shaped elements of a specific, required shape, a suitably shaped holder is used during hardening and carbonization. During carbonization, the material shrinks, and its mass, volume and density decrease. The product of carbonization has a form of shaped elements made of conductive porous carbon having an open-cell structure of the initial porous polymeric material.

It is possible to experimentally determine the relationship between the initial dimensions of the shaped element made of porous polymeric material in relation to the final, target dimensions of the shaped element made of conductive porous carbon in the function of impregnation time H, by determining its expansion during impregnation and subsequent shrinkage during carbonization. At the same time, the porosity of the shaped element made of conductive porous carbon can be experimentally determined in the function of impregnation time H. These relationships are determined separately for each polymeric material, each impregnation solution and impregnation time, by carrying out a series of control impregnation and carbonization processes and conducting experimental measurements of expanded and shrinked materials.

The above-mentioned relationships were determined for polyurethane and phenol- formaldehyde resin in a series of experiments. Experimental dependence of initial geometrical dimensions of shaped elements made of polyurethane (XA, YA, Z_a) on dimensions of the target shaped elements made of conductive porous carbon (xc, yc, zc) depends on impregnation time H:

XA = c [1,239 - 0,002 (19,89 H + 201,58) + 7,165-10^"6 (19,89 H + 201,58)² - 7,769-10^"9 (19,89 H

+ 201,58)³]

y_A = yc [1,239 - 0,002 (19,89 H + 201,58) + 7,165·10-⁶ (19,89 H + 201,58)² - 7,769·10-⁹ (19,89 H

+ 201,58)³]

ZA = zc [1,239 - 0,002 (19,89 H + 201,58) + 7,165·10-⁶ (19,89 H + 201,58)² - 7,769-Hr⁹ (19,89 H +

201,58)³]

Similarly, the porosity (P) of the shaped elements made of conductive porous carbon was determined as a function of impregnation time (H):

P = 99,7976 - 0,0058 (19,895 H + 201,583)

In order to ensure the precise shape and dimensions of the shaped elements made of conductive porous carbon, a holder is used in which impregnated shaped elements made of polymeric material are placed for hardening and carbonization. The holder ensures accurate reproduction of the target shape, which otherwise could undergo irreversible, uncontrolled deformations (e.g. surface waving) in the carbonization chamber due to the softening and drift of the resin material during the first stages of carbonization, i.e. below the temperature of 400°C. Even the shaped elements that have been thermally or chemically hardened before carbonization, undergo such deformations. According to the invention, the used holder has a suitable size and shape that transmits and maintains the desired target shape of the shaped element during the carbonization process. In addition, shaped elements placed in the holder are not exposed to any mechanical factors that could lead to their deformation. At the same time, the holder separates the carbonized shaped elements and eliminates the risk of their sticking during carbonization.

The holder can have a form of a closed vessel, then it consists of a vessel having a base and side walls, and a lid closing the vessel from above. The holder of this construction is used for carbonization of shaped elements with a complex shape and architecture. The internal space of the holder has the shape and dimensions identical to the target shape and dimensions of the shaped element made of conductive porous carbon. The impregnated shaped element made of porous polymeric material is placed inside the vessel and then covered with a lid from above. Preferably, shaped elements larger than the target dimensions of shaped element made of conductive porous carbon are placed in the vessel, taking into account experimentally determined shrinkage of the material. The use of a shaped element with dimensions larger than determined considering material shrinkage, gives the advantage that the edges of the shaped element are smoothed, and the porosity of the space at the edges locally increases. Most preferably, shaped elements made of impregnated polymeric material having dimensions 101- 200% larger than the dimensions of the target shaped elements made of conductive porous carbon are used, taking into account the experimentally determined shrinkage of the material. Preferably, the described holder has additional space at one of the edges for formation of a protrusion of the shaped element made of conductive porous carbon. This space has a smaller thickness than the remaining space of the holder, preferably 2-3 mm, so that the created protrusion has locally increased porosity in relation to the other areas of the element. This space allows to form a relief on the protrusion, used for attaching additional elements.

The holder can also have a semi-open form, limited from the bottom and from the sides, then it consists of one element containing appropriate cutouts. The handle of this construction is used for the carbonization of large-volume shaped elements, with a simple shape. The internal space of the holder has the shape and dimensions identical to the target shape and dimensions of the shaped element made of conductive porous carbon. The impregnated shaped element made of porous polymer material is placed inside the cutouts of the holder. Preferably, shaped elements larger than the target dimensions of shaped element made of conductive porous carbon are placed in the vessel, taking into account experimentally determined shrinkage of the material. The use of a shaped element with dimensions larger than determined considering - im material shrinkage, gives the advantage that the edges of the shaped element are smoothed, and the porosity of the space at the edges locally increases.

The holder can be in the form of a semi-open, limited from the bottom and the top, then it consists of two flat blocks and thickness adjusters. The holder of this construction is used for carbonization of thin shaped elements with a thickness of less than 2 cm, with a simple shape. The thickness of the adjusters is the same as the target thickness of thin shaped elements made of conductive porous carbon. The impregnated thin shaped element made of porous polymeric material is placed horizontally on the surface of one of the flat blocks, then the thickness adjusters are placed around the element, and then the it is covered from the top by the second flat block. Preferably, shaped elements having a thickness greater than the thickness of the target shaped conductive porous carbon are placed between the flat blocks, taking into account the experimentally determined shrinkage of the material. The use of a thin shaped element with a thickness greater than determined considering material shrinkage, gives the advantage that the edges of the shaped element are smoothed, and the porosity of the space at the edges locally increases. Most preferably, thin shaped elements made of impregnated polymeric material having thickness 101-200% greater than the thickness of the target thin shaped elements made of conductive porous carbon are used, taking into account the experimentally determined shrinkage of the material.

The internal surfaces of the holder, remaining during carbonization in contact with the shaped elements made of impregnated porous polymeric material, may have indentations or protrusions that form the reliefs on the surface of the shaped elements made of conductive porous carbon. The shape of these indentations and protrusions is fixed in the negative form on the surface of the shaped elements made of conductive porous carbon. This gives the possibility to design these shaped elements for possible placement of additional elements on their surface at the post-production stage.

The internal surfaces of the holder, remaining during carbonization in contact with the shaped elements made of impregnated porous polymeric material, may also have wedges that form the spatial architecture of the shaped elements made of conductive porous carbon by creating channels through the shaped elements. The shape of these wedges is fixed in a cross- section of the shaped elements made of conductive porous carbon. It gives the possibility to design these shaped elements for possible placement of additional elements in their volume at the post-production stage.

The holder can be made of any material resistant to the high temperature prevailing inside the carbonization chamber during carbonization. For example, the holder can be metallic or ceramic. Preferably, the holder is made of carbon (graphite), because such holder also has a protective function, eliminating oxygen inside the carbonization chamber, thereby preventing the corrosion of the formed shaped element made of conductive porous carbon.

A polymeric foam capable of absorbing impregnation solutions is used as a porous polymeric material for the production of shaped elements made of conductive porous carbon. Preferably, porous polyurethane foams are used. Polyurethane foams are easily available, cheap to produce, flexible and easy to form. The open-cell structure of polyurethane foams is 100% reconstituted in the structure of a conductive porous carbon formed in the process of carbonization.

Solutions of thermosetting resins or solutions of mixtures of thermosetting resins are used as impregnating material. Preferably, phenol-formaldehyde resin solutions are used, which allows to maintain the primary structure of the porous polyurethane foam, and increase of carbon content n the polymer blend prepared for carbonization. Carbonization of unimpregnated polyurethane foam leads to an amorphous carbon powder that does not maintain the macroscopic structure of the starting foam. However, it is possible to use liquid resins without diluting them in a solvent.

Preferably, an ethanol solution of a phenol-formaldehyde resin is used, because it allows to control the degree of impregnation of the porous polyurethane foam, allows a uniform supersaturation of the foam with resin and prevents blocking the open meshes due to the lower viscosity of the liquid. Commercial, liquid, unhardened phenol-formaldehyde resins require dilution with a solvent because they are too viscous, which prevents homogeneous and isotropic penetration of the resin into the hollow ribs of the porous polyurethane foam. In addition, the use of liquid and undiluted phenol-formaldehyde resins leads to blocking the meshes of polyurethane foam. Opening the mesh of impregnated polyurethane foam is problematic and time-consuming and requires, among others, its imprinting, purging or vacuum suction.

In addition to the resin solution, hardening and crosslinking agents are used, which are decomposed and/or released at an elevated temperature. Preferably, the addition of urotropine is used, which releases ammonia and formaldehyde during the thermal decomposition. Ammonia is a hardening agent, and formaldehyde is a crosslinking agent with respect to phenol- formaldehyde resins. These agents are released slowly during the thermal hardening step and allow the gradual and equilibrium hardening of the open-cell structure of the shaped elements made of impregnated porous polymeric material. Preferably, a saturated solution of urotropin is used.

Alternatively, the impregnation is carried out in solutions of thermosetting resins or solutions of mixtures of thermosetting resins without the addition of urotropin. The impregnated shaped elements made of porous polymeric material are additionally soaked in a solution of urotropin, preferably in a saturated solution of urotropin, just before the start of thermal hardening and subsequent carbonization.

The thermal hardening of the impregnated shaped elements made of porous polymeric material is carried out at a temperature of 70-180°C, preferably 120-160°C. Preferably, hardening of the shaped elements is carried out in the carbonization chamber in which carbonization will subsequently be carried out. Most preferably, the hardening step is a preliminary step of the carbonization process of the impregnated shaped elements made of porous polymer material. The carbonization process is carried out by heating the polymer material under anaerobic conditions in a closed carbonization chamber by heating it at a variable temperature, which increases during the carbonization process in the temperature range of 200-1600°C, preferably in the temperature range 700-1100°C. It is possible to conduct heating at various rates of temperature rise in the range of 0.1-15°C/min. The use of various temperature programs leads to obtaining conductive porous carbon of given physicochemical properties.

Preferably, the carbonization process is carried out using a retort having a system for the flow of a protective gas, in which the carbonized material is placed embedded in a suitably selected holder, and then it is backfilled with a protective backfill powder. Optimal carbonization conditions, allowing to obtain a material with the same properties throughout its volume, is achieved by providing a protective backfill powder that surrounds the holder uniformly from all sides, i.e. from the bottom, from the sides and from the top. In order to further optimize the process, a protective gas is passed through the retort, with the gas inlet at the bottom of the retort and its outlet at the top. Preferably, a multipoint inlet in the base of the retort and a multipoint outlet in its cover is used, which allows an even flow of protective gas throughout the entire retort volume.

The carbonization process is carried out in a closed carbonization chamber in which the polymeric material is placed. Oxygen can be removed from the carbonization chamber in any possible way, for example by covering the carbonized polymeric material with a fine layer of protective backfill powder and/or by applying a protective atmosphere of an inert gas or a reducing gas, or mixtures thereof (e.g. nitrogen, argon, carbon monoxide, hydrogen). The heating of the polymeric material shall start only after closing the carbonization chamber. The carbonization chamber can be additionally equipped with an installation for the flow of protective gas.

Fine carbonization requires the removal of traces of solvents that may have remained in the structure of the impregnated shaped elements made of polymeric material. For this purpose, prior to the start of the carbonization process, an isothermal heating of shaped elements is carried out at a temperature of 50-100°C, preferably 80°C. This heating takes 1-5 hours, preferably 2 hours. Preferably, heating to remove traces of solvents is a preliminary step in the carbonization process.

The shaped elements made of conductive porous carbon obtained by the method according to the invention are characterized by very high quality, mechanical strength and good electrical parameters. The obtained shaped elements made of conductive porous carbon are free from microcracks, and all edges of the carbon material are gently smoothened. Precise control of the dimensions and porosity of the shaped elements made of conductive porous carbon, maintaining the highest possible mechanical strength of the material, is crucial for many applications. It is possible to use the shaped elements made of conductive porous carbon obtained by the method according to the invention for the production of electrodes or current collectors to be used in a CLAB-type composite lead acid battery. The method for manufacturing of current collectors. The key to obtain current collectors of increased mechanical strength and better electrochemical parameters is production and use of a substrate with optimal parameters. Conductive porous carbon is a very good construction material due to its macroscopic structure, low mass, large specific surface area and satisfactory conductivity.

The present invention discloses production of current collectors with the use of shaped elements made of conductive porous carbon produced as described above, which allows to control their geometry, dimensions, shape, spatial architecture, relief, and porosity, without the need for their mechanical machining.

The use of shaped elements made of conductive porous carbon allows to minimize the use of lead in further stages of production of the current collectors. In addition, these shaped elements preferably have a relief in the form of indentations of a predetermined depth, forming a pattern on at least one side plane of each shaped element, and spatial architecture in the form of channels of defined dimensions and shape that go through the shaped element being the collector substrate. Preferably, the shaped elements have a protrusion with increased porosity with respect to the other parts of the substrate, which is used to form an electrical contact in the form of a strap. The protrusion may have a relief extending from its base to the top and at least one channel at the base of the protrusion running perpendicular to its relief, which serves to thread a lead tape or wire through the shaped element and hide it in the protrusion structure.

To produce the current collectors the shaped elements made of conductive porous carbon are usually used with dimensions 100mm/150mm, and 4-6 mm thick. The protrusion for producing the strap are usually 10mm/20mm, and 1-3 mm thick. The relief at the protrusion and the channel at its base are adapted to guide and hide a lead wire with a diameter of 1-2 mm or metal tape 3-8 mm wide and 0.025-0.35 mm thick.

Electrical contact. The current collector substrate of a thickness of 4-6 mm (in the form of a shaped element made of conductive porous carbon), has a rectangular protrusion of an increased porosity on one of the edges. The shape of the protrusion corresponds to the shape of the strap, its thickness is smaller than the thickness of the body of the current collector and is equal to 1-3 mm, and its dimensions are usually 10-20 mm, although it is possible to make a strap with any shape, size and location. The strap is made by the gravity casting method only within the protrusion. The protrusion is placed in a form, preferably in an aluminum form, and then it is flooded with liquid lead or a liquid lead alloy, whereupon the form cools down rapidly (by a stream of air or a stream of water), and then the formed strap is removed from the form.

Gravity casting of the strap is preferably carried out afterthe protrusion has been prepared. Through the channel at the base of the protrusion, at least one tape or wire made of lead or lead alloy is threaded, and then this tape or wire is hidden inside the relief in the side plane of the protrusion. In this way, the quality of the electrical contact is enhanced without increasing the thickness of the strap or the amount of lead or lead alloy used to prepare it. Typically, a lead tape of 3-8 mm in width and 0.025-0.35 mm in thickness or a lead wire of 1-2 mm in diameter is used. Specific solutions are applied to protrusion with a specific architecture and relief, which were previously prepared for this purpose.

It is possible to prepare a strap using any method known in the literature, that does not require the use of a substrate made of conductive porous carbon, containing a special protrusion. It is possible, among others, to carry out a gravity cast on any part of the substrate - in the form of a conductive porous carbon, for example in its corner or on the entire side edge, and then to attach a strap to this casting. It is possible to thread lead wires or tapes through the porous structure of such a substrate, joining them together and then casting the strap. It is possible to make a downhole cast into the structure of a porous substrate and attach a strap to it.

According to the present invention, electrical contact is made with use of lead or lead alloy, preferably lead or an alloy of lead and tin with tin content of 0.1-10% by weight, most preferably lead or an alloy of lead and tin with tin content in the range of 1-4% by weight. Preferably, the material with the same composition is used to make lead wire or tape elements and to make a strap casting.

Alternatively, the method according to the present invention discloses current collectors created by the combination of a porous substrate with additional solid elements increasing its strength and electrical conductivity. For this purpose, a shaped element made of conductive porous carbon is being prepared with geometry, dimensions, shape, spatial architecture, relief and porosity, corresponding to the shape, thickness and pattern of elements to be joined with. For example, a cuboidal shaped element made of conductor porous carbon is prepared with required of given external dimensions and without a protrusion used to cast a strap, but with a relief 0.5-1.5 mm deep, which pattern resembles the architecture of traditional lead grids, i.e. has a frame and lines transversely and longitudinally running through this frame. In the relief, a solid conductive carbon frame is placed, with the same pattern and thickness, so that the total thickness of the current collector does not increase. The frame should include a protrusion heading beyond the outline of the shaped element made of conductive porous carbon, that will be used for the gravitational casting of the strap according to the procedure described above.

It is also possible to combine the substrate made of conductive porous carbon having a relief, with frames made of metal, preferably lead, or alloy thereof. When using lead frames, their protrusion protruding beyond the outline of the substrate of the current collector, acts as a strap, without the need for additional casting. Preferably, frames made of lead or lead alloy are used, preferably made of an alloy of lead and tin and tin lead with tin content of 0.1-10% by weight. Most preferably lead or an alloy of lead and tin is used with tin content in the range of 1-4% by weight.

Galvanic coatings. After producing electrical contact on the carbon substrate of the current collector, a coating of lead or lead alloy is deposited on the porous material, preferably the coating of lead or an alloy of lead and tin with tin content of 0.1-10% by weight, most preferably t e coating of lead or an alloy of lead and tin with tin content of 1-4% by weight. Preferably, the same material is used to form the lead coating and electrical contact.

The lead coating may be deposited by any known method. For example, deposition by galvanic method, non-current deposition from a solution, or sputtering method is used.

Before applying the lead coating, the surface of the shaped element being used as a substrate of the current collector shall be properly degreased, i.e. all kinds of dirt and air shall be removed from its surface. It is possible to use chemical or electrochemical degreasing using known methods. Depending on the type of the substrate, the size of its surface and the degree of porosity, the time of degreasing is selected accordingly. The degreasing process ends up with rinsing the substrate in water using two types of scrubbers: a scrubber with running tap water and a manual scrubber with multi-step distilled water or deionized water.

The chemical degreasing is carried out in an alkaline bath in the presence of surfactants, for example a mixture of alkyl sulfonates. Preferably, the chemical degreasing bath is an aqueous solution containing 0.1-10 g/l NaOH and the addition of 1-100 g/l of a mixture of alkyl sulfonates. The process is carried out in a bath of pH in the rage of 6-9, preferably pH = 7.5, at 60-100°C, most preferably 70-90°C.

The electrochemical degreasing is carried out by means of an electric current with simultaneous stirring by gases evolved at the surface of the substrate. Cathodic degreasing is used with hydrogen generated on the surface of the substrate. The process is carried out in an alkaline bath, in the presence of surfactants and an ionic conductive salt (e.g., sodium carbonate). Preferably, the electrochemical degreasing bath is an aqueous solution containing 0.1-10 g/l NaOH, 20-200 g/l Na2C03, and an addition of 0.2-20 g/l of an alkyl sulfonate mixture. The process is carried out in a bath of pH in the rage of 9-12, preferably pH = 10, at ambient temperature, at a current density of 0.05-0.30 A/dm², preferably 0.15 A/dm². As an anode in electrochemical degreasing, a steel anode may be used, preferably an anode made of carbon steel. The cathode is the substrate of the current collector.

Lead coatings of the highest quality and with the best thickness control are obtained by galvanic method. Depending on the type of substrate, the size of its surface, the time and conditions of the electrolytic coating of the substrate with a metal layer are selected.

The electrolytic coating of the substrate with lead or lead alloy is carried out by mixing the electroplating solution, most preferably with mechanical or flow mixing. In the process of electrodeposition, the porous substrate of the current collector is a cathode which during the process is coated with a layer of lead or lead alloy. The anode is lead or lead alloy that dissolves during the galvanic coating process. The leading solution contains Pb(NC>3)2, preferably at a concentration of 350 g/dm³, and Pb(CH3COO)2, preferably at a concentration of 5 g/dm³. The lead coating is preferably deposited at a current density of 5 A/dcm² at a temperature of 60- 75°C. The cathode and anode should have a similar geometric surface. In order to avoid possible contamination of the galvanic bath with so-called anode slime, preferably anodes placed in protective coatings made of filter paper. The substrate coated electrolytically with lead or lead alloy is then subjected to standard rinsing processes, e.g. in a manual scrubber with multi-step distilled water or deionized water, followed by drying with the use of air flow.

The thickness of the lead layer covering the surface of the substrate of the current collector depends on whether the collector will be used to produce a negative or a positive electrode. For the negative electrode, the optimum lead layer thickness is 1-150 μιη, preferably 10-20 μιη, although it is also possible to use a lead-free carbon collector to produce a negative electrode, due to the fact that the negative electrode is reduced and the carbon collector covered with a thin layer of lead or even a bare carbon collector, it is resistant to reducing conditions even in the environment of sulfuric(IV) acid. On the other hand, for production of positive electrodes, carbon collectors with a 1-200 μηη lead layer, preferably 80-100 μιη, are needed. A thicker layer of lead on positive electrodes is needed in order to provide a collector which is stabile under highly oxidizing conditions.

To increase the conductivity and mechanical strength of the substrate of the current collector made of conductive porous carbon, it is possible to deposit an additional metal layer on it, on which the surface lead layer is then deposited. For this purpose, an additional layer of metal having good electrical conductivity is deposited, preferably a layer of copper, nickel, chromium or titanium by any known method/for example galvanic method, dry method or by spraying.

For example, an additional 5 μιη thick layer of copper is electrodeposited on a degreased carbon substrate, with use of a bath containing copper(ll) sulphate(VI) (130 g/dm³), sulfuric(VI) acid (50 g/dm³), acid hydrochloric acid (50 mg/dm³) and a mixture of surfactants LUX 400-010 (4 ml/dm³). The copper-plating is carried out at 30°C for 90 minutes at a current density of 1.0 A/dm², after which the shaped element is rinsed in deionized water.

The presence of an additional metallic layer between the carbon surface and the lead surface layer further allows the lead layer thickness to be reduced on the positive electrodes, because there is no need for a thick protective lead layer. This is also possible because the adhesion of lead to the metal substrate is much better than the adhesion of lead to carbon. This allows to reduce the mass of the entire current collector, and thus increase the specific capacity and improve the current characteristics of the lead-acid battery.

Alternatively, according to the present invention, non-metallic metal substrates, preferably made of copper, nickel, chromium or titanium are used.

Additional elements. It is possible to use additional elements that increase mechanical strength and electrical conductivity of the current collectors. This is possible due to the use of porous carbon substrates obtained by the new method according to the present invention, which allows obtaining the shaped elements made of carbon, of any specific geometry, dimensions, shape, spatial architecture, relief and porosity.

The use of a substrate with a relief allows the insertion of additional solid carbon or solid metal elements into the structure of the substrate made of carbon. These elements may be in the form of tapes, wires or frames, and preferably have a shape and size corresponding to the shape and size of the relief. Preferably, the thickness of the additional elements is less than or equal to the depth of the relief, so that the insertion of these elements does not generate an increase in the thickness of the current collector.

Insertion of the additional elements to the structure of the substrate of the current collector aims at increasing the strength and conductivity of the substrate. It is possible thanks when using a frame or elements strengthening the edges of the substrate and connecting its various parts directly with the strap.

Insertion of additional elements before covering the substrate with a lead layer allows for the formation of a uniform lead layer on the entire current collector, including the strap. It is also possible to insert additional elements into substrates covered with a layer of another metal, preferably copper, nickel, chromium or titanium.

Alternatively, it is possible to pre-coat the substrate with a lead layer, and only then to fit in its relief additional elements, preferably a frame increasing the strength and conductivity of the current collector. When inserting additional elements after covering the substrate with a layer of lead or its alloy, it is preferable to insert elements made of solid lead or covered with a lead layer.

The method for introducing an active mass into the current collector. The present invention allows efficient pasting of the current collector regardless of its construction, i.e. traditional collectors in the form of solid lead grids, and composite carbon-lead collectors.

The active mass is introduced into the collector by gravity shaking, so that it is not necessary to apply additional force to press the active mass into the open-cell structure of the current collector. The lack of additional force is crucial for the pasting of lead-carbon composite collectors, because it protects the brittle structure of the collector from cracking, breaking or crushing. An intact collector structure allows to fully use of the electrode's electrical capacity during battery operation.

Gravitational shaking is carried out using a form made of material resistant to concentrated sulfuric acid, preferably PTFE. The shape of the internal space of the form corresponds to the shape and thickness of the current collector, as well as the target shape and thickness of the electrode bar and the dimensions of the cell in the battery chamber. Thanks to this, there is no need for subsequent machining of ready-made, pasted electrodes.

The form consists of at least two elements, one of which constitutes the base and the other a frame, acting as the side walls of the form. The thickness of the frame is greater than or equal to the depth of the form. In the first case, the element containing the base of the form penetrated the frame when assembled. In the second case, the frame is embedded on the element containing the base of the frame. Assembling and disassembling the frame is simple and does not require the use of additional locks and security means. Alternatively, the form may be one- piece. Regardless of the design, the form can be used repeatedly.

The current collector is placed horizontally in a proper form, and then a suitable portion of an active mass is applied to its upper surface. The application of the active compound can be done manually or mechanically. It is advantageous to evenly distribute the active mass over the entire surface of the collector. A shaker is started, which ensures vibrations with an amplitude of 1-2 mm in the vertical plane with a frequency of 0.1-10 Hz in the vertical direction. Preferably, shaking is performed at a frequency of 0.5-5 Hz. Thanks to the applied vibrations of low frequency and significant amplitude in the vertical direction, the active mass is self-distributing over the entire volume of the collector without leaving empty spaces. The shaking is carried out for 10-500 sec, the usual time being about 1-5 minutes.

Additionally, when gravitationally shaking the paste in the collector volume, vibrations with a frequency of 10-100 Hz and an amplitude of 0.1-0.5 mm in the horizontal direction can be used as a factor accelerating the even distribution of the paste. Vertical vibrations are carried out using a vibrating table, including gravity shaking, or as an additional step after the shaking or between successive shaking phases.

In order to ensure longer life-time of the electrodes and to ensure the safety of the personnel pasting the current collectors, the pasturing takes place in a protective atmosphere, preferably inside a chamber or a vessel filled with a protective gas.

Excess of the paste, after the end of gravity shaking, is collected from the space above the top edge of the form, using the means of a doctor blade or other device of this type. The squeegee rests on the upper edges of the frame and the excess of paste is picked up horizontally, which is lifted by the doctor blade. The current collector filled with the paste, and placed in the frame, is directed to drying. It is preferable to dry the paste in the drying tunnel.

After drying the paste, the ready-made electrodes are removed from the frame. A current collector, usually after its drying, is removed from the form after it has been previously disassembled. Initial dissemblance of the form into parts significantly improves the process of electrodes removal. Usually, the electrode stays in the space in the frame opening, in which case removing the electrode requires only "pushing" it out of the frame using force perpendicular to the frame. In the case when the electrode remains connected to the base, it is possible to "push" it using a force parallel to the base. Both cases described above do not cause crushing of the electrode.

Any electroactive paste that fills the current collectors of the battery electrodes can be used for pasting. Negative paste is used for negative electrodes and positive paste for positive electrodes.

Composite lead-acid battery. The CLAB-type composite lead-acid battery according to the present invention fully exploits the potential of non-lead current collectors to increase the specific capacity of the battery, reduce its mass, improve the current characteristics and extend its life-time.

The battery according to the present invention exhibits better performance in comparison to lead-acid batteries with a standard design as well as with other non-lead current collector substrates. The battery according to the invention has a higher mechanical strength against shocks and greater electrochemical stability against repeated cycles of loading and unloading, has a more stable characteristics of potential changes over time and a smaller loss of storage capacity (the so-called shelf life).

The specific capacity of the battery according to the present invention is comparable to that of the NiCd and NiMH batteries, but in contrast thereto, the battery according to the present invention has stability against charging/discharging cycles and allows high current densities to be obtained in a short time, which is necessary for starting applications.

The battery according to the present invention uses current collectors of any defined geometry, dimensions, shape, spatial architecture, relief and porosity, produced according to the method described above.

The current collectors used in the battery have a substrate made of conductive porous carbon with increased mechanical strength and increased electrical conductivity parameters, produced according to the method described above. Conductive porous carbon used for their construction has a suitable macroscopic structure, a small mass, a large specific surface area and satisfactory conductivity. These substrates are free of microcracks, and all edges of the carbon material are gently smoothened. Thanks to this, after filling the current collector with the active mass, it is possible to fully use its entire volume, which increases the efficiency of the lead-acid battery. The carbon shaped elements can be additionally reinforced by means of additional elements fitted into the relief of their relief.

The use of porous carbon substrates obtained by the present method gives the possibility to create current collectors for composite lead-acid batteries of any size, shape and electrical capacity. Thanks to this, the designers of vehicles and other devices will not be limited by the shape of the battery. Among the potential applications of the battery according to the invention, it is possible to replace starting batteries, power batteries of electric and hybrid vehicles, including bicycles and scooters, and stationary energy stores (so-called power wall). In addition, the lead-acid battery technology is cheap and environmentally friendly, and the CLAB-type batteries themselves can be recycled with efficiency of up to 100%.

The current collectors used in the battery usually have 100mm/150mm, and a thickness of 4-6 mm, which allows the use of standard starter battery housings. The straps, which are the electrical contact of the collector, are gravity cast on special protrusion of the carbon substrates, which makes it possible to minimize the amount of lead used to build the battery, and thus further reduce its mass.

These collectors are filled with an appropriate active mass, positive or negative, depending on the type of electrode and collector. The active mass is introduced according to the method described above, which does not expose the collectors to mechanical damage during the pasting process.

The solutions according to the present invention have been laboratory tested. The method for manufacturing of shaped elements made of conductive porous carbon, a method for manufacturing of current collectors, a method for introducing an active mass into the current collector of the lead-acid battery electrode, and the composite lead-acid battery according to the present invention are described below in working examples presenting preferred embodiments.

Example 1. A 5cm/5cm/5cm polyurethane shaped element was subjected to 7 hours impregnation in a 50wt.% solution of phenol-formaldehyde resin in ethanoi with an addition of urotropin. The impregnated polyurethane shaped element was measured and weighed. As a result of the impregnation, the dimensions of the polyurethane shaped element increased (diastole) by 29.3% in each dimension. The obtained impregnated polyurethane was subjected to thermal hardening. For this purpose, it was embedded in a graphite one-piece holder and placed in a retort made of heat-resistant steel. The steel retort after closure with a steel lid was placed inside the closed chamber furnace and heating was started with an argon flow of 2800 ml/minute. The heating was started at room temperature, the temperature was raised to 80°C and held for 3 hours to drive off residual ethanoi. Subsequently, the temperature was raised to 130°C and held for 2 hours to harden the impregnated polyurethane shaped element. Then, the carbonization process was started. For this purpose, the heating of the impregnated shaped element placed in the steel retort was continued. The furnace temperature was raised to 1050°C for 420 minutes at an average rate of temperature rise of 2.5°C/minute. After reaching 1050°C, the temperature was maintained for additional 60 min, after which the oven was turned off and allowed to cool. The furnace was opened after it was cooled to room temperature and a steel retort was removed. The carbonization product embedded in the graphite holder was removed from the retort. The protective backfill was retained for reuse. A molded conductive porous carbon was removed from the graphite holder and then measured and weighed. It was observed that the dimensions of the shaped element were reduced (shrinkage) in relation to the dimensions of the impregnated polyurethane shaped element by 22.1% in each dimension. The carbonization yield was determined to be 45% by weight based on the ratio of the product weight to the weight of the impregnated polyurethane shaped element.

Example 2. A 2cm/5cm/6cm polyurethane shaped element was subjected to 2 hours impregnation in a 50wt.% solution of phenol-formaldehyde resin in ethanoi with an addition of urotropin. The impregnated and hardened polyurethane shaped element was measured and weighed. As a result of the impregnation, the dimensions of the polyurethane shaped element increased (diastole) by 22.5% in each dimension. The obtained impregnated polyurethane was subjected to thermal hardening. For this purpose, it was embedded inside a closed graphite holder and placed in a ceramic retort and covered with a protective backfill powder made of pre- milled charcoal with a grain size of 2.0-4.0 mm. The impregnated polyurethane shaped element constituted 34wt.% while the protective backfilling powder was 62wt.% of the batch volume of the retort. The protective backfill powder tightly covered the impregnated polyurethane shaped element with 5 cm thick layer. After closing the ceramic retort was placed inside a closed chamber furnace and heating was started with a nitrogen flow equal to 120 ml/min. Heating was started at room temperature and continued until the temperature reached 1050°C for 3600 minutes, with an average rate of temperature rise of 0.3°C/min. After reaching 1050°C, the temperature was maintained for additional 400 minutes, after which the oven was turned off and allowed to cool. The furnace was opened after it was cooled down to room temperature and a steel retort was removed. The carbonization product placed in the graphite holder was removed from the retort after removing the protective backfill powder. The protective backfill was retained for reuse. A shaped element made of conductive porous carbon was removed from the graphite holder and then measured and weighed. It was observed that the other dimensions of the shaped element were reduced (shrinkage) in relation to the dimensions of the impregnated polyurethane shaped element by 19.4%. The carbonization yield was determined to be 36% by weight based on the ratio of the product weight to the weight of the impregnated polyurethane shaped element.

Example 3. A 0.5cm/5cm/8cm thin polyurethane shaped element was subjected to 2 hours impregnated in a 58wt.% solution a phenol-formaldehyde resin in ethanol. The impregnated polyurethane shaped element was measured and weighed. As a result of the impregnation, the thickness of the polyurethane shaped element increased (diastole) by 22.0%, while other dimensions increased by 19.0%. The impregnated shaped element made of porous polymeric material was soaked in a saturated solution of urotropin for 20 seconds. The obtained impregnated polyurethane shaped element was subjected to thermal hardening. For this purpose, it was embedded in the holder between graphite flat blocks, using graphite thickness adjusters with a thickness of 0.5 cm. The holder provided constant pressure of the graphite blocks to the impregnated polyurethane shaped element. The shaped element in the holder was placed in a retort made of heat-resistant steel and covered with protective backfill powder made of pre- ground coke with a grain size of 3.0-5.0 mm. The impregnated polyurethane shaped element constituted 30%, while the protective backfilling powder was 60% of the batch volume of the retort. The protective backfill powder tightly covered the impregnated polyurethane shaped element with 8 cm thick layer. The steel retort after closure with a steel lid was placed inside the closed chamber furnace and heating was started without the flow of any gaseous medium. The heating was started at room temperature and the temperature was raised to 90°C, which was maintained for 2 hours to drive the residual ethanol. Thereafter, the temperature was raised to 150°C and held for 1 hour to harden the impregnated polyurethane shaped element. Then, the carbonization process was started. For this purpose, the heating of the impregnated shaped element placed in the steel retort was continued. The furnace temperature was raised to 1050°C for 420 minutes with an average rate of temperature rise of 2.5°C/min. After reaching 1050°C, the temperature was maintained for additional 60 minutes, after which the oven was turned off and allowed to cool. The furnace was opened after it was cooled down to room temperature and a steel retort was removed. The carbonization product embedded between the graphite flat blocks of the holder was removed from the retort after removal of the protective backfill powder. The backfill was retained for reuse. A thin shaped element made of conductive porous carbon was removed from the graphite holder and then measured and weighed. It was observed that the thickness of the shaped element made of conductive porous carbon was equal to the size of the thickness adjusters of the holder, while in the other dimensions the size of the shaped element was reduced (shrinkage) in relation to the dimensions of the impregnated polyurethane shaped element by 16.5%. The carbonization yield was determined to be 38% by weight based on the ratio of product weight to the original weight of the impregnated polyurethane shaped element.

Example 4. A 0.6cm/10cm/10cm thin polyurethane shaped element was subjected to 12 hours impregnation in a 25wt.% solution a phenol-formaldehyde resin in ethanol. As a result of the impregnation, the thickness of the polyurethane shaped element increased (diastole) by 20.0%, while other dimensions increased by 25.0%. The impregnated shaped element made of porous polymeric material was soaked in a saturated solution of urotropin for 20 seconds. The obtained impregnated polyurethane shaped element was subjected to thermal hardening. For this purpose, it was embedded in the holder between graphite flat blocks, using graphite thickness adjusters with a thickness of 0.6 cm. The holder provided constant pressure of the graphite blocks to the impregnated polyurethane shaped element. The shaped element in the holder was placed in a silicon carbide retort and covered by protective backfill powder made of pine sawdust with a grain size of 1.0-18 mm. The impregnated polyurethane shaped element constituted 12%, while the protective backfilling powder was 84% of the batch volume of the retort. The protective backfill powder tightly covered the impregnated polyurethane shaped element with a 13 cm thick layer. The retort after closure of the lid was placed inside a closed chamber furnace and heating was started with an argon flow of 200 ml/min through the retort. Heating was started at room temperature and continued until the temperature reached 1050°C for 3600 minutes with an average rate of temperature rise of 0.3°C/min. After reaching 1050°C, the temperature was maintained for additional 400 minutes, after which the oven was turned off and allowed to cool. The furnace was opened after it was cooled down to room temperature and a steel retort was removed. The carbonization product embedded between the graphite flat blocks of the holder was removed from the retort after removal of the protective backfill powder. The protective backfill was retained for reuse. A thin shaped element of conductive porous carbon was removed from the graphite holder and then measured and weighed. It was observed that the thickness of the shaped element made of conductive porous carbon was equal to the size of the thickness adjusters of the holder, while in that the other dimensions of the size of the shaped element was reduced (shrinkage) in relation to the dimensions of the impregnated polyurethane shaped element by 19.0%. The carbonization yield was determined to be 40wt.% based on the weight ratio of the product to the impregnated polyurethane shaped element.

Example 5. Positive electrode current collector. A cuboidal shaped element made of conductive porous carbon of dimensions 100mm/150mm/5mm and porosity 20 ppi with a 10mm/20mm/2mm protrusion was prepared by cutting out a cuboidal shaped element made of porous polyurethane of dimensions 120mm/180mm/6mm with a 12mm/24mm/6mm protrusion, which has been subjected to 7 hours impregnation in a 50wt.% solution a phenol- formaldehyde resin in ethanol with an addition of urotropin. After drying, it was placed in a holder in the form of a vessel with a lid with a cuboidal inner space of 100mm/150mm/5mrn, with additional space of 10mm/20mm/2mm for protrusion. The shaped element embedded in the holder was placed in a closed retort and covered with a protective backfill powder evenly from all sides, the entire retort was placed in the furnace, the argon flow was started through the retort of 2800 ml/min, after which heating was started in the regime: 2 hours at 80°C, 3 hours at 120°C, 7 hours at 1050°C, with an average rate of temperature rise of 2.5°C/min. The furnace was cooled down to room temperature. The formed shaped element made of conductive porous carbon was then used a substrate of the current collector. The shaped element was subjected to chemical degreasing for 1 hour at 80°C in a solution of sodium hydroxide (1 g/l), with the addition of a mixture of alkyl sulphonates (40 g/l), and then washed with deionized water. On the protrusion, a strap was gravitationally casted using lead-tin alloy with tin content of 2%. In the next stage, the carbon substrate was subjected to electrochemical degreasing in a solution containing sodium hydroxide (1 g/l), sodium carbonate (100 g/l), a mixture of alkyl sulfonates (2 g/l) at a current density of 0.15 A/dm² for 60 seconds at room temperature, after which the substrate was rinsed, successively in the flow and manual scrubbers. The prepared substrate was subjected to electrodeposition of a surface layer of lead-tin alloy (tin content 2%) with a thickness of 100 μηη, at a current density of 1.6 A/dm². The lead alloy deposition was run at 28°C for 190 minutes. A methanesulfonic bath containing lead methanesulfonate (95 g/l), tin methanesulfonate (2.5 g/l), methanesulfonic acid (65 g/l), acetaldehyde (0.75 g/l) was used. During the electrodeposition, the shaped element was a cathode, while the anode was a lead-tin (2% tin) alloy electrode. After the completion of galvanization, the carbon substrate with lead-tin layer and an electrical contact (current collector) was rinsed in the hand scrubber with deionized water and dried in air flow.

Example 6. Positive electrode current collector. A cuboidal shaped element made of conductive porous carbon of dimensions 100mm/120mm/5mm and a porosity of 18 ppi with a 10mm/20mm/lmm protrusion was prepared by cutting a cuboidal shaped element made of porous polyurethane with dimensions of 150mm/180mm/7mm, and an additional cardboard grid element of 100mm/120mm/lmm with a 10mm/20mm/l mm protrusion. The shaped element and grating were subjected to a 6 hours impregnation with a 50wt.% solution of phenol- formaldehyde resin in ethanol. After the impregnation, the two elements were immersed for 20 seconds in ethanolic saturated solution of urotropin, after which the impregnated shaped element was placed in a holder in the form of a vessel with a cuboidal inner space, dimensions 100mm/150mm/5mm with protrusions 1 mm high corresponding to the shape of the grid, and the grid was placed in a holder in the form of two flat blocks with 1 mm thickness adjusters, after which both elements embedded in the holders were placed in a closed retort and covered with a protective backfill powder evenly from all sides, and the entire retort was placed in the furnace, after which heating was started in the regime: 3 hours at 70°C, 2 hours at 130°C, 6 hours at 1200°C, using an average rate of temperature rise of 1.5°C/min. The furnace was cooled to room temperature. The shaped element made of conductive porous carbon with 1 mm relief was juxtaposed with a conductive carbon grating with a thickness of 1 mm, and the shaped element was used as a substrate of the current collector. On the protrusion, a strap was gravitationally casted using lead-tin alloy with tin content of 2%. The shaped element was subjected to chemical degreasing for 1 hour at 80°C in a solution of sodium hydroxide (1 g/l), with the addition of an alkyl sulfonate mixture (40 g/l), then washed with deionized water and then subjected to electrochemical degreasing in a solution containing sodium hydroxide (1 g/l), sodium carbonate (100 g/l), mixture of alkyl sulfonates (2 g/l) at a current density of 0.15 A/dm² for 60 seconds at room temperature, after which the substrate was rinsed in water repeatedly distilled, successively in flow and manual washers. The prepared substrate was subjected to electrodeposition of a surface layer of lead-tin alloy (tin 2%) with a thickness of 80 μιη, with a current density of 1.6 A/dm². The lead alloy deposition was ru n at 28°C for 152 minutes. A methanesulfonic bath containing lead methanesulfonate (95 g/l), tin methanesulfonate (2.5 g/l), methanesulfonic acid (65 g/l), acetaldehyde (0.75 g/l) was used. During the electrodeposition, the shaped element was a cathode, while the anode was a lead-tin alloy (2% tin) electrode. After the completion of galvanization, the carbon substrate with lead-tin layer and an electrical contact (current collector) was rinsed in the hand scrubber with distilled water and dried in air flow.

Example 7. The negative electrode current collector. A cuboidal shaped element made of conductive porous carbon of dimensions 100mm/150mm/5mm and porosity of 20 ppi with a 10mm/20mm/2mm protrusion was prepared by cutting out a cuboidal shaped element made of porous polyurethane of dimensions 120mm/180mm/6mm with a 12mm/24mm/6mm protrusion. An additional cardboard grid element of dimensions 100mm/150mm/0.5mm was cut. The shaped element and the grid were subjected to a 6.5 hours impregnatio n in a 50wt.% solution of phenol-formaldehyde resin in ethanol with and addition of urotropine. The impregnated shaped element was placed in a holder in the form of a vessel with a cuboidal inner space, dimensions 100mm/150mm/5mm with protrusions 0.5 mm high corresponding to the shape of the grid, and with additional space for a 10mm/20mm/2mm protrusion. The grid was placed in a holder in the form of two flat blocks with 0.5 mm thickness adjusters, after which both elements embedded in the holders were placed in a closed retort and covered with a protective backfill powder. The retort was placed in the fu rnace, and heating was started with an average rate of temperatu re rise of 0.3°C/min until the temperatu re reached 1050°C, after which the temperature was maintained for additional 8 hours. The furnace was cooled to room temperature. The shaped element made of conductive porous carbon with 0.5 mm relief was juxtaposed with a grid made of conductive carbon of a thickness of 0.5 mm, and the joined shaped element was used as substrate of the current collector. On the protrusion, a strap was gravitationally casted using lead. The shaped element was subjected to chemical degreasing for 1 hour at 80°C in a solution of sodium hydroxide (1 g/l), with the addition of a mixture of alkyl sulfonates (40 g/l), followed by electrochemical degreasing in a solution containing sodium hydroxide (1 g/l) , sodium carbonate (100 g/l), a mixture of alkyl su lphonates (2 g/l) at a current density of 0.15 A/dm² for 60 seconds at room temperature, after which the substrate was rinsed in deionized water. The prepared substrate was subjected to electrodeposition of 5 μιτι copper layer in a bath containing copper(ll) sulfate(VI) (130 g/dm³), sulfuric(VI) acid (50 g/dm³), hydrochloric acid (50 mg/dm³) and a mixture of su rfactants LUX 400-010 (4 ml/dm³). Copper deposition was carried out at 30°C for 90 minutes at a cu rrent density of 1.0 A/dm², after which the shaped element was rinsed. Then, the surface of the fitting was covered with a 10 μιτι thick lead layer, with a current density of 1.2 A/dm². Lead deposition was carried out at 25°C and for 32 minutes. A methanesulfonic bath containing lead methanesulfonate (130 g/l), methanesulfonic acid (65 g/l) was used. Du ring the electrodeposition, the shaped element was a cathode, while the anode was a lead electrode. After the completion of galvanization, the carbon substrate with copper layer, lead surface layer and an electrical contact (current collector) was rinsed in the hand washer with deionized water and air dried.

Example 8. The negative electrode cu rrent collector. A cuboidal shaped element made of conductive porous carbon of dimensions 100mm/120mm/5mm and porosity of 22 ppi with a 10mm/20mm/2mm protrusion was prepared by cutting a cuboidal shaped element made of porous polyurethane of dimensions 150mm/180mm/7mm with a 15mm/30mm/7mm protrusion. The shaped element was subjected to 8 hours impregnation in a 50wt.% solution of phenol-formaldehyde resin in etha nol with and addition of urotropine. The impregnated shaped element was placed in a holder in the form of a vessel with a cuboidal inner space, dimensions 100mm/120mm/5mm with protrusions 0.2 mm high and wide forming a shape of rays propagating frim the base of the protrusion. The holder had an additional space for a 10mm/20mm/2mm protrusion with 0.2 mm deep protrusions and a wedge at the base of the projection. The shaped element was embedded in a holder, placed in an oven and covered with a protective backfill powder evenly from all sides, after which heating was started under a regime of: 3 hours at 70°C, 2 hours at 130°C, 6 hours at 1200°C, an average rate of temperature rise of 2°C/min between successive stages was applied. In the 0.2 mm deep relief of the shaped element wires made of lead-tin alloy (tin content 2%) of a diameter of 0.2 mm were fitted. This shaped element was used as a su bstrate of the current collector. Through the channel at the base of the protrusion a tape made of lead-tin alloy (tin content 2%) with a thickness of 0.2mm was threaded into the relief of the protrusion, and a lead-tin strap (tin content 2%) % was gravitationally cast on the protrusion. The shaped element was subjected to chemical degreasing for 1 hou r at 80°C in a solution of sodium hydroxide (1 g/l), with the addition of a mixture of alkyl sulfonates (40 g/l), then washed with deionized water and then subjected to electrochemical degreasing in a sol ution containing sodium hydroxide (1 g/i), sodium carbonate (100 g/l), mixture of a lkyl sulphonates (2 g/l) at a cu rrent density of 0.15 A/dm² for 60 seconds at room temperatu re, after which the substrate was rinsed in water deionized water. The prepared su bstrate was covered with a layer of lead-tin alloy (tin content 2%) with a thickness of 10 μιη at a cu rrent density of 1.2 A/dm². Lead deposition was carried out at 25°C for 32 minutes. A methanesulfonic bath containing lead methanesulfonate ( 130 g/l), tin methane sulfonate (3.4 g/l), methanesulfonic acid (65 g/l), acetaldehyde (0.75 g/l) was used. During the electrodeposition, the shaped element was a cathode, while the anode was a lead electrode. After the completion of galvanization, the carbon substrate with copper layer, lead surface layer and an electrical contact (current collector) was rinsed in the hand washer with deionized water and air dried.

Example 9. Current collectors with unconventional shapes. A tubular shaped element made of conductive porous carbon with a diameter of 20 mm and a height of 50 mm, and tube shaped element made of conductive porous carbon with an inner diameter of 21 mm, an outer diameter of 30 mm and a height of 50 mm were prepared by cutting out shaped elements made of porous polyurethane of dimensions, respectively: a cylinder of diameter 25 mm and height 60 mm and tubes with an inner diameter of 21 mm, an outer diameter of 35 mm and a thickness of 60 mm. Additional elements were cut out from 1 mm thick cardboard in the form of a circle with a diameter of 20 mm and a ring with an inner diameter of 21 mm, an external diameter of 30 mm, both with perpendicular protrusions of 5mm/10mm/lmm. All elements were subjected to 7 hours impregnation in a 50wt.% solution of phenol-formaldehyde resin in ethanol with and addition of urotropine. The impregnated shaped elements were juxtaposed together and placed in holders in the form of vessels with a lid with an internal space of dimensions identical with the target dimensions of the shaped elements. Hardening and carbonization as well as casting of the electrical contact on the splines, degreasing and lead deposition were carried out as in Examples 1-4.

Example 10. The positive electrode collector was pasted with a positive paste. The collector was in the form of a cuboidal shaped element made of conductive porous carbon coated with a 100 μιη lead/tin alloy layer with a tin content of 2wt.%. The shaped element had dimensions of 150mm/100mm/4mm and a porosity of 20 ppi. In addition, the shaped element had an electrical contact form of so-called strap made of lead/tin alloy with a tin content of 2wt.%. The collector was placed inside a two-element frame made of PTFE with internal dimensions of 151mm/101mm/5mm, which was equipped with an additional notch for the strap. The form was placed on a gravitational shaker standing on a vibrating table. A portion of the positive paste with a volume of about 120 cm³ (with an excess of about 60 cm³) was applied to the surface of the collector and subjected to

3 minutes shaking using vertical vibrations of 5 Hz and an amplitude of 1.5 mm. During vibrations, the vibrations were switched on horizontally at a frequency of 50 Hz and an amplitude of 1 mm. After the end of shaking, the collector was dried, and then the ready electrode was pulled out of the mold after it had been disassembled into parts. The obtained electrode was subjected to electrochemical tests. Positive readings indicated the proper and even distribution of the paste in the entire volume of the current collector. The current collector was placed inside the cell of the composite carbon-lead-acid battery and subjected to use.

Example 11. A CLAB-type composite lead-acid battery was a system of six cells with a voltage of 2 V, connected in series to each other, giving a potential of 12 V. Together, each battery cell consists of two positive electrodes and two negative electrodes arranged alternately. As the current collectors of the electrodes were used shaped elements made of conductive porous carbon with dimensions of 118mm/100mm/4 mm, with an electrical contact in the form of a strap being gravitationally casted on the protrusion of the surface. The collectors of the negative electrodes on the entire surface were subjected to electrodeposition of 10 μιη lead layer, while the positive electrode collectors were electrodeposited with 100 μιτι lead and tin alloy layers with tin content of 1.5%. The collectors were filled with the appropriate active mass (negative or positive depending on the type of electrode) by means of the gravitational shaking method using the two-element PTFE form. Positive electrodes were enveloped with a polypropylene separator. In each cell of the battery, the electrodes with the same sign were connected in parallel. The electrolyte was 37.5% sulfuric(VI) acid with a density of 1.28 g/cm³, approximately 420 ml electrolyte was used in each cell. The battery was assembled in a commercial battery housing measuring 215mm/130mm/200mm (length/height/width), allowing the electrolyte to mix between the cells. The housing had a lid provided with electrical pole outlets and valves that discharged gases generated during battery operation. The total weight of the battery was 10.5 kg. The following satisfactory battery parameters were obtained: rated voltage 12 V, theoretical capacity 40 Ah.

Example 12. Prototype CLAB-type composite lead-acid type battery with non-standard shape had a single cell with a voltage of 2 V. As the current collector of the negative electrode a tubular shaped element made of conductive porous carbon was used with a diameter of 20 mm and a height of 50 mm, set through its base with an additional element of conductive carbon in the form of a circle with a diameter of 20 mm and a thickness of 1 mm, having a protrusion of 5mm/10mm/lmm. As a positive current collector, a porous conductive tube shaped with an inner diameter of 21 mm, an outer diameter of 30 mm and a height of 50 mm is used, juxtaposed through its base with an additional element made of conductive carbon in the form of a ring with an inner diameter of 21 mm, outer diameter 30 mm and 1 mm thick, having a protrusion of 5mm/10mm/lmm. Electrical contacts were gravitationally casted on the protrusion. The collector of the negative electrode on the whole surface was subjected to electrodepositing of a 10 μιτι lead layer, while the positive electrode collector was covered with a 100 μηη lead and tin alloy layer with a tin content of 1.5% over the entire surface. The collectors were filled with the appropriate active mass (negative or positive depending on the type of electrode) by means of the gravitational shaking method using the two-element PTFE form. The positive electrode was enveloped with a polypropylene separator. The target was compiled by inserting a roller-shaped negative electrode inside a tube-shaped positive electrode. The electrolyte was 37.5% sulfuric(VI) acid with a density of 1.28 g/cm³. Fire placed in a specially made plastic housing in the form of a cylinder with a diameter of 35 mm and a height of 80 mm. The cell was flooded, approximately 30 ml of electrolyte was used in each cell. The housing was semi-open. The total battery weight was approximately 150 g. The following satisfactory battery parameters were obtained: rated voltage 2 V, theoretical capacity 0.5 Ah.

Claims

1. A method for manufacturing of shaped elements made of conductive porous carbon, using the process of carbonization of polymeric materials, consisting of heating in a gaseous environment a polymeric material impregnated with a suitable resin or a mixture of resins, that undergoes thermal hardening followed by carbonization in an anaerobic or reducing atmosphere, characterized in that a porous polymeric material is subjected to mechanical pre-treatment to obtain shaped elements made of a porous polymeric material (1) having the desired geometry, taking into account the expected dimensional changes during the carbonization process, which are then impregnated with a resin or a mixture of resins (2), then the impregnated shaped elements (3) are optionally subjected to further mechanical machining, and next the shaped elements (3) are hardened, then embedded in the holder (4), the whole is placed in the carbonization chamber (5) and carbonized, which results in formation of shaped elements made of conductive porous carbon (7) of a required, target geometry without the need for their further mechanical machining.

2. A method for manufacturing of shaped elements according to claim 1, characterized in that the machining of a shaped element made of porous polymeric material (1) or impregnated shaped element made of porous polymeric material (3) comprises a mechanical treatment of a single piece of the polymeric material or a mechanical treatment and juxtaposition of two or more pieces of the polymeric material with the same or different porosity.

3. A method for manufacturing of shaped elements according to claim 1, characterized in that porous polyurethane or cellulose-based materials are used as the porous polymeric material (1); a thermosetting resin, preferably containing a phenol-formaldehyde resin, is used as the resin or the mixture of the resins (2); impregnation with a thermosetting resin is carried out in a resin solution, preferably in an ethanolic resin solution at a concentration of 10-60% by weight, preferably 20-50% by weight, optionally with the addition of urotropine; the impregnation time is not less than one hour, preferably 6 hours, to obtain an impregnation degree A > 300%; and the impregnated shaped elements made of polymeric material are soaked, prior to thermal hardening in a solution of urotropin, preferably in a saturated ethanolic solution of urotropin, for 5-200 seconds, preferably 20 seconds.

4. A method for manufacturing of shaped elements according to claim 1, characterized in that the desired, target shape and size of the shaped elements made of conductive porous carbon (7) is obtained by using a holder (4) of a suitably fitted size and shape that transmits and maintains the desired shape of the original shaped element during the carbonization process, wherein it is preferable to use shaped elements (3) with dimensions larger than the target dimensions of the shaped elements (7), taking into account the experimentally determined shrinkage of the material, most preferably 101-200% larger than the target dimensions of shaped elements made of conductive porous carbon (7), including experimentally determined shrinkage of the material.

5. A method for manufacturing of shaped elements according to claim 4, characterized in that as a holder (4) :

- is used a holder consisting of a vessel (4a) having a base, and side walls, and a lid (4b), which holder has an inner space of identical shape with the target shape of the shaped elements made of conductive porous carbon (7), and the impregnated shaped element (3) placed inside the vessel (4a) and then covered with a lid (4b) from above; or

- is used a holder consisting of a block holder (4c) comprising cutouts (4d) having the shape identical to the target shape of shaped elements made of conductive porous carbon (7), and the impregnated shaped element (3) is placed in the cutouts (4f); or

- in the case of thin shaped elements made of conductive porous carbon (7) with a thickness of not more than 2 cm, preferably 0.2-1.0 cm thick, is used a holder consisting of two flat blocks (4e) and thickness adjusters (4f), of a thickness identical to the ta rget thickness of thin shaped elements made of conductive porous carbon (7);

which holder (4) is made of graphite, carbon material, metal or ceramic material; and additionally, the internal surfaces of the holder (4) staying in contact with the shaped elements (3) and (7) have indentations (4g) or protrusions (4h) shaping the relief (8) on the surface shaped elements made of conductive porous carbon (7), or have wedges (4i) shaping the spatial architecture of the shaped elements made of conductive porous carbon (7) creating respective channels (9) going through these shaped elements (7).

6. A method for manufacturing of shaped elements according to claim 1, characterized in that the desired shape and size of the shaped elements made of porous conductive element (7) can also be obtained by mechanical machining of the porous polymeric material (1) or the impregnated porous polymeric material (3), where the relationship between the geometric dimensions of the shaped elements made of porous polymer material (1) and shaped elements made of conductive porous carbon (7) (XA/XC, YA/YC ZA/ZC), and the relationship between the geometric dimensions of the impregnated shaped elements made of porous polymer material (3) and shaped elements made of conductive porous carbon (7) (XB/XC, YB/VC, ZB/ZC), is determined experimentally for each polymer, impregnation agent and impregnation time (H), with the experimentally determined dependence of the dimensions of the shaped elements, using polyurethane and phenol-formaldehyde resin, independent of the direction in space and is:

XA = xc [1,239 - 0,002 (19,89 H + 201,58) + 7,165-10^~5 (19,89 H + 201,58)² - 7,769·10-⁹

(19,89 H + 201,58)³]

y_A = yc [1,239 - 0,002 (19,89 H + 201,58) + 7,165·10-⁶ (19,89 H + 201,58)² - 7,769-10^"9

(19,89 H + 201,58)³]

z_A = zc [1,239 - 0,002 (19,89 H + 201,58) + 7,165-ΗΓ⁶ (19,89 H + 201,58)² - 7,769-H)-⁹

(19,89 H + 201,58)³]

the porosity (P) of the shaped elements made of porous conductive carbon (7) is determined by monitoring the impregnation time, where the dependence of porosity on the impregnation time is determined experimentally for each polymer, impregnation and impregnation time (/-/), using polyurethane and phenol resin formaldehyde experimentally determined relationship between porosity and H impregnation time is:

P = 99,7976 - 0,0058 (19,895 H + 201,583)

7. A method for manufacturing of shaped elements according to claim 1, characterized in that the impregnated shaped elements made of porous polymeric material (3) are thermally hardened in a carbonization chamber (5) at a temperature of 70-180°C, preferably 120- 160°C, after which they are carbonized, preferably in the same carbonization chamber (5) at a temperature above 200°C, preferably in a temperature range of 200-1600°C at a heating rate of 0.1-15.0°C/min, preferably 1.5-2.5°C/min, wherein, after completion of the carbonization process, slow cooling of the shaped bodies made of conductive porous carbon (7) to 25°C takes place with an average speed of l-2°C/min.

8. A method for manufacturing of shaped elements according to claim 7, characterized in that the carbonization of the impregnated shaped elements made of porous polymeric material (3) is carried out with an isothermal preliminary step lasting 1-5 hours, preferably 2 hours, at a temperature of 50-100°C, preferably 80°C; and as the carbonization chamber (5), a closed furnace chamber or retort (10) with a lid (11) is used, which is placed in a closed furnace chamber, the anaerobic atmosphere during the carbonization stage being obtained using a carbon-rich protective backfill powder (6), oxygen scavenging, preferably including hard coal, fine coal, brown coal, charcoal, coke, granular activated carbon, powdered activated carbon, technical carbon black or biomass, preferably wood or sawdust, or anaerobic atmosphere during the carbonization step is obtained by the use of a protective or reducing atmosphere, preferably by using nitrogen, argon, carbon monoxide, hydrogen, helium, neon, krypton or xenon; alternatively, as the carbonization chamber (5), a retort (10) with a lid (11) is used, which is placed in a closed furnace chamber, the retort (10) having a protective gas flow arrangement with a multipoint gas inlet in the retort base (10) and a multi-point gas outlet in the cover (11), and the impregnated shaped elements made of porous polymeric material (3) embedded in the holder (4) are surrounded by a protective backfill evenly from all sides.

9. A method for manufacturing of current collectors of a composite lead-acid battery, the collector having a substrate made of porous non-lead conductive material, coated at least partially with lead or lead alloy and having an electrical contact, characterized in that the substrate made of porous non-lead conductive material used has increased mechanical strength, and was previously made in a form of shaped elements with a specific, required target geometry, dimensions, shape, spatial architecture, relief and porosity, in a way that does not require mechanical machining of the conductive material from which the substrate is made of, where the substrate of the current collector can have any desired shape, preferably the shape of a rectangular thin plate, a round shape, a ring shape, a cylindrical shape, a tube shape, and also has a relief in the form of indentations of a predetermined depth, forming a pattern on at least one of its lateral planes and spatial architecture in the form of channels of defined dimensions and shape going through the substrate of the collector, and preferably a protrusion on one of the collector's walls, for preparation of an electrical contact, preferably a cuboidal protrusion with an increased porosity compared to the porosity of the remaining parts of the substrate, which protrusion preferably has a relief extending from its base to the top, and in addition preferably the collector has at least one channel at the base of the protrusion perpendicular to its relief.

10. A method for manufacturing of current collectors according to claim 9, characterized in that the substrate of the current collector is supplemented by additional elements increasing its mechanical strength or electrical conductivity, preferably by fitting into its relief a solid grid made of a conductive material, which grid has a pattern corresponding to the relief pattern and a thickness preferably corresponding to the depth of the relief which the solid grid preferably has a protrusion extending beyond the outline of the substrate of the current collector, used for preparation of an electrical contact.

11. A method for manufacturing of current collectors according to claim 9, characterized in that the electrical contact in the form of a strap is made by a gravity casting, by pouring liquid lead or liquid lead alloy into the current collector located in a form, preferably in an aluminum form, and then rapidly cooling the frame down and removing the formed strap out of the form, wherein the strap is cast on a rectangular protrusion on the side edge of the substrate, preferably after having been threaded through at least one hole at the base of the protrusion, at least one tape or wire made of lead or lead containing alloy, and concealing the tape or wire within the relief in the plane lateral of the protrusion.

12. A method for manufacturing of current collectors according to claim 9, characterized in that the surface of the substrate of the current collector is completely or partially coated with a lead layer, preferably by galvanic method, by non-current deposition from the solution or by a sputtering method, wherein the thickness of the lead layer covering the substrate surface of the negative electrode current collector is 1-150. μητι, preferably 10-20 μιη, and the thickness of the lead layer covering the substrate surface of the positive electrode current collector is 1-200 μιη, preferably 80-100 μηι; and the current collector's substrate covered with a lead layer is preferably supplemented with additional elements increasing its mechanical strength or electrical conductivity, preferably by fitting into its relief a solid grid of lead material, which grid has a pattern corresponding to the relief pattern and a thickness preferably corresponding to the depth of the relief, which the solid grid preferably has a strap-shaped protrusion extending beyond the outline of the current collector constituting an electrical contact.

13. A method for manufacturing of current collectors according to claim 12, characterized in that for producing an electrical contact, for covering the surface of the substrate of the current collector with a lead layer, and for making the grids of lead material, the same material is used, i.e. lead or lead-containing alloy, preferably lead or an alloy of lead and tin with tin content of 0.1-10% by weight, most preferably lead or an alloy of lead and tin with tin content in the range of 1-4% by weight, and the current collector substrate of porous non-lead conductive material and the solid grating of non-lead conductive material are made of conductive carbon, glassy carbon, copper , nickel, chromium, titanium or conductive carbon coated with a layer of copper, nickel, chromium or titanium, or glassy carbon covered with a layer of copper, nickel, chromium or titanium.

14. A method for introducing an active mass into the current collector of a positive or a negative electrode of lead-acid battery, which collector is equipped with an electrical contact made of lead or lead alloy, employing a form with an inner shape and depth identical with the target shape of said electrodes, which form is made of a material resistant to sulfuric(VI) acid, preferably of PTFE, characterized in that the active mass is introduced by gravitational shaking, and an excess of the paste located above the upper edge of the form is collected by means of a doctor blade;

wherein the applied mechanical vibrations in the vertical direction have frequency of 0.1-10 Hz, preferably 0.5-5 Hz, and an amplitude of 1-2 mm, which mechanical vibrations are produced by a mechanical device periodically striking the bottom of the frame; and in addition, a device generating a mechanical vibration with a frequency of 10-100 Hz and an amplitude of 0.1-0.5 mm in the horizontal direction is used, realized by an additional mechanical device, preferably a vibrating table;

and the shape of the inner space of the frame corresponds to the shape and thickness of the current collector and the target shape and thickness pasted electrode and the dimensions of the cell in the battery compartment, and the form comprised of at least two elements, preferably of a base and a frame forming the side walls of the frame, the thickness the frame is greater than or equal to the depth of the frame, and pasted current collector is removed from the frame after its previous dissemblance, wherein an active mass is introduced into the collector in a protective atmosphere, preferably under nitrogen atmosphere.

15. A lead-acid composite battery having at least one cell comprising at least one positive electrode, at least one negative electrode, electrolyte and means ensuring current flow, at least one electrode having a current collector made of porous non-lead substrate covered at least partially with a surface layer of lead or its alloy, and filled with an appropriate active, cathodic or anodic active mass, characterized in that the current collectors of the electrodes have substrates made of porous non-lead conductive material of increased mechanical strength, previously made in the form of shaped elements with a specific, required target geometry, dimensions, shape, spatial architecture, relief and porosity, in a way that does not require mechanical machining of the conductive material from which the substrate is made of, wherein:

- substrates of a porous non-lead conductive material with improved mechanical strength, preferably substrates made of conductive porous carbon with increased mechanical strength, are manufactured according to the method described in claims 1-8; - the current collectors of the electrodes are manufactured according to the method described in claims 9-13;

- the active mass is introduced into the current collector of the electrode according to the method described in claim 14.