# Patent

## Title
Optimised energy storage device having capacitor material on lead based negative electrode

## Abstract

A lead-acid battery comprising: —at least one negative electrode comprising lead-based battery electrode material and at least one region of capacitor material overlying the lead-based battery electrode material, each electrode being in electrical connection to an outer terminal of the battery, and —at least one positive lead-dioxide based battery electrode, each positive electrode being in electrical connection to a second outer terminal of the battery, —separator interleaving the facing electrodes; —electrolyte filling at least the space of the electrodes and separators wherein the capacitor material overlying the lead-based battery electrode material comprises 20-65% by weight of a high electrical conductivity carbonaceous material, 30-70% of a high specific surface area carbonaceous material, at least 0.1% lead and binder.

## Background
This application is the U.S. national phase of International Application No. PCT/AU2008/000405 filed 20 Mar. 2008, which designated the U.S. and claims priority to AU Application No. 2007901466 filed 20 Mar. 2007, the entire contents of each of which are hereby incorporated by reference.
BACKGROUND
The present invention relates to energy storage devices, including batteries such as lead-acid batteries.
There is growing demand for the development and introduction of vehicles that do not rely almost entirely on fossil fuels, to combat air pollution in urban environments and to reduce the global consumption of limited supplies of the fossil fuels. Such vehicles fall into three main classes: fuel-cell vehicles (FCVs), electric vehicles (EVs), hybrid electric vehicles (HEVs). There are several types of hybrid electric vehicles, namely, micro-, mild-, medium- and full-hybrid. The battery voltage of the hybrid electric vehicles increases in the order: 12 V in micro hybrid, 36 V in mild hybrid, 144 V in medium hybrid and over 200 V in full hybrid. On the other hand, the battery capacity decreases in the order: 50-60 Ah in micro hybrid, 15-20 Ah in mild hybrid, 6-8 Ah in medium hybrid and 6 Ah in full hybrid.
Electric vehicles and hybrid electric vehicles may use a variety of different battery types, including lead-acid batteries. Micro and Mild hybrid electric vehicles may use mainly lead-acid batteries because of reduced cost. Hybrid electric vehicles rely on a combination of an internal combustion engine and a battery for power supply. The hybrid electric vehicles provide some advantages over the existing internal combustion engine cars, including higher use of the electrically generated power, resulting in lower emissions and less fuel consumption.
Whilst there have been many significant advances in the development of new batteries and power networks for vehicles relying at least partly on electric power, the batteries used in these vehicles still suffer from a number of problems.
In all of these batteries, different demands are placed on the battery in terms of the current drawn from and recharged to the battery at various stages during vehicle operation. In the case of vehicle applications, as one example, a high rate of discharge is needed from the battery to enable acceleration in electric vehicles, or acceleration as well as engine cranking in hybrid electric vehicles. A high rate of recharging of the battery is associated with regenerative braking. In such high rate applications (and in high charging applications for the batteries) the battery preferably needs to be able to supply the high rate of discharge over a period of 1 minute or more.
In the situation where lead-acid batteries are utilized, particularly in hybrid electric vehicles, the high rate of battery discharging and recharging results in the formation of a layer of lead sulphate on the surface of the negative plate, and the generation of hydrogen/oxygen at the negative and positive plates. This largely arises as a result of high current demands on the battery. The partial state-of-charge conditions (PSoC) under which these batteries generally operate is 20-100% for electric vehicles, 40-70% for medium and full hybrid electric vehicles, and 70-90% for micro and mild hybrid electric vehicles. This is a high rate partial state-of-charge (HRPSoC). Under simulated HRPSoC duty, such as hybrid electric vehicle operations, the lead-acid batteries fail prematurely mainly due to the progressive accumulation of lead sulphate on the surfaces of the negative plates. This occurs because the lead sulphate cannot be converted efficiently back to sponge lead during charging either from the regenerative braking or from the engine. Eventually, this layer of lead sulphate develops to such an extent that the effective surface area of the plate is reduced markedly, and the plate can no longer deliver the higher current demanded from the automobile. This significantly reduces the potential life span of the battery.
In other technology fields, it would be advantageous to provide alternative battery types that offer improved overall lifespan and performance whilst catering for the different power demands on the battery.
Accordingly, there exists a need for modified batteries, such as lead-acid batteries, that have an improved life span and/or improved overall performance compared to current batteries. There is also a need to identify components of the battery that can be modified to improve performance, in terms of a balance of capacity and lifespan.
SUMMARY OF THE INVENTION
According to one aspect, there is provided a lead-acid battery comprising:

    
    
        at least one negative electrode comprising lead-based battery electrode material and at least one region of capacitor material overlying the lead-based battery electrode material, each electrode being in electrical connection to an outer terminal of the battery,
        at least one positive lead-dioxide based battery electrode, each positive electrode being in electrical connection to a second outer terminal of the battery,
        separator interleaving the facing electrodes, and
        electrolyte filling at least the space of the electrodes and separators
    
    


wherein the capacitor material overlying the lead-based battery electrode material comprises 20-65% by weight of a high electrical conductivity carbonaceous material, 30-70% of a high specific surface area carbonaceous material, lead and binder.
Preferably the lead content in the capacitor material is at least 0.1% by weight.
Preferably the binder is present in an amount of between 1-30% by weight, preferably 5 and 20% by weight.
The capacitor material may further comprise fiber reinforcement material in an amount of from 0 to 10% by weight.
According to one embodiment, the capacitor material consists of 21-65% high electrical conductivity carbonaceous material, 35-65% high specific surface area carbonaceous material, 3-40% lead, 5-20% binder and 2-10% fiber reinforcement material.
It has been found that the layer-configuration provides the optimal working of the battery, particularly with the amounts of carbonaceous materials in the capacitor material described above. Moreover, it has been found that the capacitor material of each negative electrode should constitute between 1 and 15% by weight of the negative battery electrode material. Below 1% is insufficient for minimum performance requirements of the device. Above 10% it has been found that saturation is reached, such that the further weight increase does not further increase performance. Nevertheless, other than cost and weight consideration, an increase in the mass of capacitor material above 10% is acceptable to a level of about 15%.
It has been found that layer-configuration provides the substantial area of cohesive interface between capacitor material and battery material which is formed through the reaction with lead battery material and carbonaceous capacitor material, resulting in enhanced mechanical strength and reduced electrical resistance of the electrode. Along with these beneficial effects, a greater lead content in the capacitor material is transferred during operation from the battery material directly contacting with capacitor material which controls electrode potential enough to depress gassing.
It has been found that for most effective operation, a layer of capacitor material overlies all effective areas of the negative electrode that face a positive electrode. Generally, negative electrodes in lead acid batteries comprise a current collector (which may be in the form of a grid), which is coated on both faces with lead-based battery electrode material. Although only parts or single-faces of the negative electrode may be overlaid by capacitor material, it is preferred that the negative electrode comprises a current collector coated with lead-acid battery material, and a layer of capacitor material overlying each face of lead-acid battery material that is opposite to a positive electrode.
It is noted that during production, prior to application of the capacitor material onto the negative battery electrode material-coated negative electrode, this electrode may be formed or unformed.
Preferably, the capacitor material overlying the lead-based battery electrode material has a porosity of between 50-90%.
According to one embodiment, the positive electrode will generally comprise a positive current collector (which may be in the form of a grid), formed from a lead alloy. Preferably the lead alloy comprises 0.005-0.015% by weight Ba, 0.03-0.08% by weight Ca, 0.4-2.2% by weight Sn, and lead. Preferably lead constitutes the balance of the alloy material. This alloy material is most suited as it has high corrosion resistance for batteries of the claimed type.
The battery may be a valve regulated lead acid battery. Preferably in this battery type the battery comprises absorptive glass microfibre or absorbed glass mat (AGM) separators between adjacent electrodes. Further, the valve regulated lead acid battery preferably has a pressure on electrodes of between 20 and 100 kPa.
When the battery is of the valve regulated lead acid-type, this is preferably operated at between 95-60% State-of-charge (SoC), but it may be between 95-30% SoC.
The battery may be of the flooded electrolyte type. In this case, it is preferred that the pressure on the electrodes is between 5 and 45 kPa. In this embodiment, it is preferred that porous polymer separators such as porous polyethylene membrane separators be located between adjacent positive and negative electrodes. The porous polyethylene separators may optionally further comprise unwoven fibrous material reinforcement.
When the battery is of the flooded electrolyte type, it is preferably operated at between 98-80% SoC. In automotive applications, the vehicle preferably comprises the flooded electrolyte battery, internal combustion engine and an alternator, and provides electricity to the vehicle for idle, stop and start operations.
Preferably, the lead-acid battery comprises an alternating series of positive and negative electrodes.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic side view of a lead-acid battery in accordance with one embodiment of the invention.
FIG. 2 is a schematic plan view of the lead-acid battery of FIG. 1.



DETAILED DESCRIPTION OF THE INVENTION
The present invention will now be described in further detail with reference to preferred embodiments of the invention.
To avoid any doubt, except where the context requires otherwise due to express language or necessary implication, the word “comprise” or variations such as “comprises” or “comprising” is used in an inclusive sense, i.e. to specify the presence of the stated features but not to preclude the presence or addition of further features in various embodiments of the invention.
General Features
The term “lead-acid battery” is used in its broadest sense to encompass any unit containing one or more lead-acid battery cells.
The lead-acid batteries described contain at least one negative electrode comprising a coating of lead-based battery electrode material and at least one overlying region of capacitor material, and at least one lead dioxide-based positive electrode.
Electrode Structure
Electrodes generally comprise a current collector (otherwise known as a grid or plate), with the active battery electrode material applied thereto. The active battery electrode material is most commonly applied in a paste form to the current collector, and in the present specification the term paste applies to all such active-material containing compositions applied in any way to the current collector. The term “based” used in the context of electrodes is intended to refer to the active electrode material. This term is used to avoid suggesting that the electrode is formed entirely from the active material, as this is not the case. The term also is intended to indicate that the active material of the given electrode may contain additives or materials other than the active material specifically mentioned.
Electrodes
The negative and positive electrodes (prior to application of capacitor material) may be of any arrangement or type suitable for use in a lead-acid battery. Generally, such electrodes are in the form of a current collector or metal grid (usually made from lead or lead alloy) that supports the electrochemically active material (lead or lead dioxide) which is pasted onto the grid. The operation of pasting is well known in the field. It is to be noted that, prior to formation of the battery, the active material may not be in the active form (i.e. it may not be in the form of the metal, or in the dioxide form). Thus, the terms encompass those other forms which are converted to lead metal or lead dioxide when the battery is formed.
Current Collector (Grid) Alloy
The device lifespan is controlled primarily by the positive electrode, the substrate of which may be exposed to corrosion potential. Corrosion results in internal resistance increase, growth or creep deformation of the grid, which results in battery shortage or loss of the integrity of the device, and finally destruction of the electrode structure.
To avoid these problems, it has been found that it is advantageous to use the following alloy for the positive electrode current collector or grid: 0.05-0.08% calcium, 1-2% tin, optionally barium, and the balance lead (by weight).
The negative electrode current collector or grid preferably comprises 0.06-0.12% by weight calcium, 0-1% by weight tin, and the balance lead, or 1-2% tin, with the balance lead, or lead alone.
Capacitor Material
Capacitor material is applied to at least one region of the negative electrode, overlying the negative battery electrode material. The capacitor electrode material is commonly applied as a paste comprising the capacitor material components in a liquid (water or organic).
The capacitor material comprises a high Specific Surface Area (SSA) carbonaceous material in an amount of 30-70% by weight. These high specific surface area carbonaceous capacitor materials include activated (or active) carbon, carbon nanoparticles or nano carbon including carbon nano tube (CNT), mesoporous carbon and mixtures thereof. Specific surface areas of between 1000 and 3000 m2/g, preferably 1000-2500 m2/g. Currently, for cost reasons, activated carbon, which is not generally conductive, is a convenient source.
The high electrical conductivity carbonaceous materials that are present in the capacitor material in an amount of between 20-65 weight %, include carbon black, graphite, carbon nanotubes (CNT), vapour phase grown fibre or whisker, graphite fibres, and mixtures thereof. Carbon black is a powdered form of elemental carbon and is made by a range of processes, and any such carbon blacks may be used. Examples of different carbon blacks include acetylene black, channel black, furnace black, lamp black and thermal black, the surface area of which is less than 1000 m2/g, far less than that of activated carbon.
However, some nano-carbons like CNT are conductive with fairly large surface area of around 1000 m2/g, in case of which such carbon can work as one body of the above-mentioned two types of carbonaceous materials.
Capacitor carbonaceous materials are chemically carbon as a whole including impurities and foreign elements and radicals for intentional modification. Typical examples are functional radicals on the surface of activated carbon and boron in carbon black particles which are possibly usable.
Typical particle sizes for carbon blacks are 10-400 nm, although they tend to form aggregates of about 100-800 nm in size.
The capacitor material typically further comprises a binder. Any binders known in the art can be used, such as styrene butadiene rubber (SBR), chloroprene rubber, polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), neoprene and carboxymethyl cellulose (CMC), or a mixture thereof. The binder is suitably used in an amount of 1-30% by weight of the capacitor mixture, preferably 5-20% by weight.
The capacitor material may also comprise a fibre reinforcement material (FRM). Fibre reinforcement materials with an aspect ratio of 20-500 are preferred. Suitable materials include plastic fibres such as polyester fibres (PE), polyethylene terepthalate (PET), polypropylene, polyacrylonitrile, as well as carbon or graphite fibres and vapour-grown whiskers. These fibres may be of between 1-30 μm in diameter, and 0.05-2 mm long. They suitably constitute 0-10% by weight of the capacitor material.
The capacitor material further comprises lead, preferably in a content of at least 0.1%, preferably 3-40% enabling control of negative potential. Through the potential change of the electrode, the lead component will either be in the metallic state or in an oxidised state as a compound with a counterion such as sulphate, in particulate form and/or adsorbed on the carbon surfaces.
Application of Capacitor Material
The capacitor material is suitably applied onto the negative battery electrode material as a layer. A viscous mix composed of the capacitor material and water or solvent can be coated by varied methods such as doctor blade, roll coater, dip coater and so on. Another application technique is adhesion or lamination by using a pre-formed sheet of capacitor material. From viewpoint of manufacturing, the preferred pre-formed sheet comprises capacitor material coated on porous thin sheet, such as a paper sheet, an unwoven sheet of plastic or glass fiber, and so on.
Before preparing the mix, at least a portion of the components of the capacitor material are mixed by milling, abrasion, grinding, dispersion, mixing or similar. This retains optimally high battery and capacitor functionality with compactness and high energy density. Furthermore, the resulting interface between the battery and capacitor material layers enables the optimal structure and property of the negative electrode to be achieved through the reactions of lead and carbon.
The thickness of the capacitor material (as a weight % of the total negative material mass—battery and capacitor) is preferably between 1% and 15%. Below 1% the capacitor layer is too thin to provide the advantages of hybrid performance. Hybrid performance becomes saturated at 10% by weight (of the negative material mass). Above this level increased capacitor material mass does not continue to improve performance, but can be tolerated up to 15% by weight.
Porosity of the capacitor material is required for ionic transport, and is essential for both the capacitor layer and the underlying battery negative battery material. This is particularly required when the capacitor material overlies 90% or more of the surface area of the negative battery electrode material. Porosity is preferably 50-90%.
The capacitor material is applied as a paste in a liquid, the liquid being evaporated away after application of the paste. The components are mixed and dispersed in a liquid such as water or organic solvent. Other additives may be included in the paste composition, especially binders, such as CMC, MC, PVA and polyacrylate. For organic pastes, NMP may be used as the solvent.
Physical Configuration
The electrodes may be of any suitable shape, and therefore may be in flat-plate form or in the form of a spirally-wound plate for the formation of either prismatic or spirally-wound cells. For simplicity of design, flat plates are preferred. The current collector is preferably in the form of a grid.
Electrolyte
In the case of lead-acid batteries, any suitable acid electrolyte may be used. The electrolyte may, for instance, be in the form of a liquid or a gel. Sulphuric acid electrolyte is preferred.
The electrolyte can contain additives such as alkaline or alkaline earth sulphates for the prevention of shortage and corrosion. Aluminum content is effective to keep the life-span of the battery. Aluminum content is preferably 0.01-0.3 mol/L of Al ion, or 5-50 g/L of Al2(SO4)3.18H2O.
Busbars or Conductors
The busbar of the lead-acid battery may be of any suitable construction, and may be made from any suitable conductive material known in the art. The term “connected to” used in the context of the busbars refers to electrical connection, although direct physical contact is preferred. In the case where the battery is not of a typical lead-acid battery configuration with busbars, any conductor may be used that does not involve circuitry external to the battery.
Other Battery Features
Generally, the components of the battery will be contained within a battery case with further features appropriate to the type of battery employed. This includes outer terminals (positive and negative) for electrical connection to the battery. The lead-acid battery may be of a flooded-electrolyte design or of a valve-regulated design. Where the lead-acid battery is a valve-regulated lead-acid battery, the battery may be of any suitable design, and may for instance contain gel electrolyte. Specific features of the battery unit appropriate to such designs are well known in the art of the invention.
The pressure that may be applied to the lead-acid plate group may lie in the range of 5-45 kPa for flooded electrolyte design, and from 20-100 kPa for valve regulated lead-acid battery design. The pressure has to be on the all faces of the plates, preferably equally, in order to protect mechanically the porous electrodes and therefore spacers of solid sheet or elastic body can be inserted between the container wall and the group.
Separators
Generally, each of the positive and negative electrodes is separated from adjacent electrodes by porous separators. Separators are particularly important when pressure is applied across the electrodes.
The separators maintain an appropriate separation distance between adjacent electrodes and maintain group pressure. Separators located between adjacent electrodes may be made from any suitable porous material commonly used in the art, such as porous polymer materials including polyethylene, unwoven fibrous materials and absorptive glass microfibre (“AGM”). For valve regulated lead acid batteries, AGM separators are preferred. For flooded electrolyte type batteries, the separators are preferably chosen from polymer membranes, such as polyethylene (PE) membranes which may optionally be reinforced with unwoven fibrous materials. Polyethylene separators are suitably between 1 and 1.5 millimeters thick, whereas AGM separators can be between 0.8 and 2.5 millimeters thick.
Formation of Lead Acid Batteries
The electrodes of lead-acid batteries need to be “formed”. This can take place either in bulk with like electrodes prior to assembly of the battery (“tank formation”) or in the assembled battery. The formation operation is well known in the field. It is to be understood that the references to “lead-based” and “lead dioxide-based” materials are used to refer to lead or lead dioxide itself, materials containing the metal/metal dioxide or to materials that are converted into lead or lead dioxide, as the case may be, at the given electrode.
As is indicated by the language used above, the lead-acid battery contains at least one of each type of electrode. The number of individual cells (made up of a negative and positive plate) in the battery depends on the desired voltage of each battery. For a 36-volt battery appropriate for use as a mild hybrid electric vehicle battery (which may be charged up to 42 volt), this would involve the use of 18 cells.
Functions and Features
The devices of the present application work advantageously well under partial state-of-charge (PSOC) conditions, while some features like charge and discharge performance are better than conventional lead acid batteries. Under PSOC, sulfation or hard PbSO4 crystal growth is subdued, enabling operation under PSOC cycling for a large throughput and to keep device operational during PSOC long rest periods. Charge acceptance and deep discharge performance are substantially enhanced, which is on the same course of PbSO4 characteristics. Furthermore, the existence of a capacitor region enhances the reactivity of battery reaction, resulting in capacity improvement. PSOC is practically divided into 2 ranges, 80-98% SOC and 50-80%. The former shallow PSOC is for discharge performance and later deep PSOC is for recharge or regenerative performance.
Both VRLA and flooded versions can be used in the wide variety of secondary battery applications, including automotive and industrial (stationary, and traction) applications.
While flooded lead acid batteries are nowadays used as automotive SLI (conventional starting-lightening-ignition) batteries, the flooded version described herein in PSOC can now be used in these applications, and provide further advantages such as idling stop, regenerative braking and start assist, all of which are required for good fuel economy in automotive vehicles. Such hybrid electric vehicles (HEV) using flooded electrolyte batteries are called micro-HEV. Although VRLA versions of the battery also work well, the flooded version has the two advantages of low cost and large heat capacity. Automotive batteries are generally mounted in the underhood engine compartment, where the battery is exposed to much heat flow from the engine and electric circuits. VRLA batteries of smaller heat capacity are prone to thermal runaway and accelerated water loss. Therefore VRLA versions of the batteries should be mounted in the trunk/boot room area. In this application PSOC is as shallow as 80-98%, preferably 90-98%.
The VRLA version of this battery for automotive applications has a deeper PSOC, so it works well for regenerative braking to recover braking energy, which improves fuel economy. This is suitable for use in a type of HEV, referred to as mild-HEV.
EXAMPLES
A lead-acid battery of one embodiment of the invention is illustrated schematically in FIGS. 1 and 2. It is noted that for ease of explanation, the illustrated battery has fewer cells than the number of cells that would typically be contained in a commercial form of the battery.
The battery comprises three lead dioxide positive plate electrodes (1) and two negative electrodes (2). The negative electrodes comprise a current collector or grid (3) with a lead-containing battery electrode paste composition applied to it (4) and capacitor material paste applied onto the surfaces of lead negative material (5). This includes the faces of the electrode that are opposite the positive electrodes.
Formation of the electrode is conducted in the manner known in the art. In a variation on this embodiment that is simpler to manufacture, a lead based negative electrode is prepared with lead pasted by conventional techniques to the main body section in lead paste material, and, after it is cured and dried, the capacitor material is pasted (eg by dipping) onto the surfaces of this lead based negative electrode. Formation may take place before or after application of the capacitor electrode material. The positive (1) and negative electrodes (2) are positioned in an alternating arrangement in a battery case (6).
The positive lead dioxide electrodes (1) and negative electrodes (2) of the embodiment illustrated in FIG. 1 are 76 millimeters wide by 76 millimeters high by 0.8-1.7 millimeters thick. The capacitor material region (5) of the negative electrode takes up 0.5 millimeters of the thickness of the negative electrode, or up to 10% by weight of the negative battery electrode material.
Separators (7) are located between the adjacent electrodes. Absorptive glass microfibre (AGM) separators (7) of 1.1 millimeters in thickness are positioned between the positive (1) and the negative electrodes (2).
The battery case (6) is filled with sulfuric acid solution (8). The positive electrodes are connected to a positive busbar (9), and the negative electrodes connected to a negative busbar (10).
Example 1—E1
A monoblock battery (87 mm W×150 mm L×110 mm H) of 6 cells in a VRLA arrangement was constructed with following components, processes and conditions;
Negative electrode: grid (Pb with 0.1% Ca) of 76 mm W×76 mm H×1.4 mm thickness, 5 plates/cell
Aqueous mix (density 4.0) of lead oxide, expander, polyester fiber and sulfuric acid was applied to grids, cured, dried and then tank formed according to conventional methods.
The capacitor mix is composed of
















Carbon black (furnace black)
43 mass parts



Active carbon (SSA 2300 m2/g)
38



Polyester fiber (20 μm diameter,
 5



aspect ratio 150)



Chloroplane rubber
10



CMC
 4



Water
280□ based on




the 100 mass




parts of 100%




solids content.










The mix is applied onto both sides of all formed plates by the doctor blade method and dried. Capacitor mass was 5% of total negative active mass (dry base) with 75% porosity.
Positive electrode: grid (Pb with 0.035% Ca, 0.007% Ba, 1.8% Sn) of 76 mm W×76 mm H×1.7 mm thickness, 4 plates/cell.
Aqueous mix (density 4.2) of lead oxide, sulfuric acid and polyester fiber is applied to the grid, cured, dried and tank formed according to conventional methods.
Separator: AGM 1.1 mm thick
6 groups of both electrodes interleaved with AGM were connected in a cast-on-strap (COS) machine and inserted into 6 cells with group pressure of 60 kPa, and sealed, and then electrolyte was poured in.
Electrolyte: sulphuric acid aqueous solution of specific gravity 1.30 containing 30 g/L of Al2(SO4)2.18H2O.
Activation was conducted as follows:

    
    
        Constant-current charge of 1 A for 15 hr;
        Constant-current discharge of 2 A until voltage down to 10.5V;
        Constant-current charge of 1 A for 15 hr;
        Capacity in 5 hr-rate was measured as 10.2 Ah.
    
    


After activation, a battery for study was dismantled, the capacitor-layer was chemically analysed and the electrode section was examined by EPMA. The lead content was 1.9% and distributed in a way that the lead was enriched near the interface of the battery and capacitor-masses.
Battery capacity of discharge was measured at 5 hr rate.
Reference Example 1—R1
In place of the negative electrode of Example 1, the negative electrodes were prepared to have a type of reference configuration as follows:

    
    
        A half area of the negative electrode was pasted with the battery mix, and the other half was pasted with the capacitor mix. The halves were a left-hand side and a right-hand side, coated on both faces with the battery material, or capacitor material, respectively.
    
    


Reference Example 2—R2
In place of the container used in Example 1, new larger one (87 mmW×220 mmL×110 mmH) was used to insert the following plate group composed of the battery and capacitor portions keeping the same group pressure of 60 kPa. The battery portion was the same to above E1 and capacitor portion was composed of the 5 capacitor negative electrodes and 4 positive electrodes alternatively arranged in series and interleaved with AGM of 0.5 mm thickness. The both electrodes were constructed with 0.6 mm thick lead sheet substrates with 45% punched-openings by coating capacitor and positive battery mixes, respectively and the dry thicknesses of the negative and positive electrodes were about 0.9 and 0.7 mm thick, respectively. The substrates were the same alloys as E-1. The mass of capacitor material was 5% by weight of the battery material. The positive electrode was tank-formed before stacking and assembling.
All negative and positive electrodes were welded (COS) to be electrically connected in parallel, respectively, and inserted into 6 cells and sealed. Then electrolyte was poured in. Activation was conducted similarly.
Capacities were measured and results were listed as follows:















Energy Density



Capcity@5 hr-Rate
(Relative)





















E-1
10.2
Ah
100%



R-1
5.2

51%



R-2
10.1

68%










Coating the capacitor layer onto the lead acid battery plate can have the benefits of the lead acid battery plate providing energy, while the capacitor electrode gives power. E-1 with layered configuration shows clearly the highest values, compared with the other two configurations.
Example 2—E2
The above Examples 1 was repeated, but with the following changes:
Composition of Capacitor Mix
















Acetylene black in place of furnace
25 mass %



black



Active carbon (SSA 1900 m2/g)
62%



Vapor-grown carbon whisker
3%



SBR
7%



Carboxy methyl cellulose
3%



Water
300%










Mass of the capacitor layer was 10% of total negative mass and porosity was 65%.
The results of capacity and cycle life are shown in Table 1
Example 3—E3
The above Example 1 was repeated, but with the following changes:
Composition of Capacitor Mix
















Furnace black
30 mass %



Expanded graphite
15 mass %



Active carbon (SSA 1900 m2/g)
44%



Polyester fiber 20 μm diameter,
3%



aspect ratio 150



SBR in place of Chloroplane
6%



Carboxy methyl cellulose (CMC)
3%



Water
300%










Mass of capacitor layer was 8% and porosity was 65%.
The results are shown in Table 1.
Example 4—E4
The above Example 1 was repeated, but with the following changes:
Composition of Capacitor Mix
















Acetylene black
23 mass %



Vapor grown carbon whisker
11



(fibre)



Active carbon (SSA 2300 m2/g)
15



Active carbon (SSA 1200 m2/g)
37



Polyester 20 μm diameter aspect
4



ratio 150



SBR
7



CMC
3










The mass of capacitor layer was 10% and porosity was 65%.
The results are shown in Table 1.
Example 5—E5
The above Example 1 was repeated, but with the following changes:
Mass of capacitor layer was 2% with 65% porosity.
Example 6—E6
The above Example 1 was repeated, but with the following changes:
Capacitor coating was applied onto only one side of the plates. The mass was 5% of total negative mass.
Example 7—E7
The above Example 1 was repeated, but with the following changes:
















Carbon black (Furnace black)
22 mass %



Active carbon (SSA 2300 m2/g)
69%



Carbon whisker (same as E-2)
3%



Chloroplane rubber
4%



CMC
1%










Example 8—E8
The above Example 1 was repeated, but with the following change:
















Carbon black (Furnace black)
65 mass %



Active carbon (SSA 2300 m2/g)
30%



Polyester fiber (same as E-4)
1%



Chloroplane rubber
3%



CMC
1%










Example 9—E9
In place of the positive grid alloy in E-1, an alloy without Ba was used. The electrolyte did not contain Al additive.
Alloy element: Sn 1.5 mass % Ca 0.06% Al 0.002%
Reference Example 3—R3
The above Example 1 was repeated, but with the following changes:
No capacitor material coating was applied.
Reference Example 4—R4
The above Example 1 was repeated, but with the following changes:
















Carbon black (Furnace black)
65 mass %



Active carbon (SSA 2300 m2/g)
20%



Polyester fiber (same as E-4)
5%



Chloroplane rubber
7%



CMC
3%










Reference Example 5—R5
The above Example 1 was repeated, but with the following changes:
















Carbon black
17 mass %



Active carbon (SSA 1900 m2/g)
72%



Polyester fiber (same as E-4)
4%



Chloroplane rubber
5%



CMC
2%










Reference Example 6—R6
In place of the layered coating in E-1, 5% of dried and pulverized capacitor mix was added to the negative battery mix.
With regard to above batteries, battery performance for hybrid electric vehicle applications (HEV) was tested as follows:
Cycle pattern: Battery was discharged in 2 A for 1 hr reaching 80% SOC, then
500 sets of discharge of 50 A for 1 sec and charge of 20 A for 1 sec were applied,
then 510 sets of charge of 30 A for 1 sec and rest for 1 sec.
The above sets in series were counted as 1 cycle and cycle life was determined when battery voltage reached 0V.
After the test of E1, the lead content and its distribution through the capacitor layer section was checked. It was confirmed that lead impregnation proceeded up to 30.2 weight % on average. Hereafter lead content in the capacitor mass is calculated as an average of the before- and after-values.
The results are shown in Table 1.












TABLE 1







Sample
Capacity
Cycle life
Pb Content























E-1
10.2
Ah
820
cycle
16.1%



E-2
9.9

830

17.7



E-3
10.1

750

14.9



E-4
10.4

850

17.0



E-5
9.7

620

13.0



E-6
9.6

500

10.9



E-7
10.0

520

9.9



E-8
9.9

510

11.1



E-9
10.2

640

12.7



R-1
5.2

190

0.9



R-2
10.1

580

6.8



R-3
9.3

180

□



R-4
9.7

340

8.8



R-5
9.7

310

7.6



R-6
9.9

410

—










All examples of this invention had a longer cycle life under PSOC operation. E-9 using a conventional Ba-free alloy has a shorter life, due to the positive grid corrosion and resulting increased internal resistance. Regarding the reference examples, R-3 of conventional battery (Control) without capacitor material showed the poorest result. R-4 and R-5 with capacitor material outside the levels claims performed poorer.
R-1 and R-2 with an electrode configuration different from outside the claimed configuration, which were poorer in energy density as previously mentioned, showed shorter life. It is postulated that this is related to the non-existence of the interface between the battery- and capacitor-materials. R-6 containing the mixture of both battery and capacitor materials was also poor in PSOC cycle life.
Example 11—E11
A monoblock battery (126 mm W×236 mm L×200 mm H) of 6 cells (JIS B24 size) in flooded arrangement was constructed with following components, processes and conditions:
Negative electrode: grid (Pb with 0.1% Ca) of 102 mm W×108.5 mm H×1.5 mm thickness, 7 plates/cell
Aqueous mix (density 4.0) of lead oxide, expander, polypropylene fiber and sulfuric acid was applied to the grids, cured and dried according to conventional methods.
The Capacitor mix is composed of:
















Carbon black (furnace black)
43 mass %



Active carbon (SSA 2300 m2/g)
38%



Polypropylene fiber (15 μm
5%



diameter, aspect ratio 100)



Chloropteane rubber
10%



CMC
4%



Water
280%










The capacitor mix is applied onto both sides of all plates by the doctor blade method and dried. The capacitor mass was 5% of total negative active mass (dry base) with 75% porosity.
Positive electrode: grid (Pb with 0.035% Ca, 0.007% Ba, 1.8% Sn) of 102 mm W×108.5 mm H×1.7 mm thickness, 6 plates/cell
Aqueous mix (density 4.2) of lead oxide, sulfuric acid and polyester fiber is applied to grid, cured and dried according to conventional methods.
Separator: Porous polyethylene (PE) sheet covered with an unwoven glass fiber layer, 1.0 mm thick
Electrolyte: sulfuric acid with specific gravity 1.24.
After enveloping positive plates with separator sheet, 6 groups of both plates were connected in a COS machine and then inserted into 6 cells of a monoblock container with group pressure of 20 kPa. A cover-plate was welded on and then electrolyte was poured in. Then container formation was conducted in the water bath of 35° C. applying total electricity (76 Ah), that is 180% of theoretical value, for the period of 10 hrs.
Battery capacity was measured as 42.0 Ah at 5 hr-rate.
Battery performance for automotive idling stop cycle was tested as follows:
















Discharge
 45 A for 59 sec and 300 A for 1 sec



Charge
100 A for 60 sec @ 14.0 V










Above discharge-charge was repeated 3600 cycles followed by resting for 48 hr. This procedure was continued in the 25° C. environment until battery voltage reduced down to 7.2V—that is the cut-off voltage for cycle life.
The results are shown in Table 2.
Example 12—E12
The above Example 11 was repeated, but with the following changes:
Group pressure was set as 40 kPa, and electrolyte was added with 15 g/L of Al2(SO4)3.18H2O.
Example 13—E13
The above Example 11 was repeated, but with the following changes:
Group pressure was changed to 8 kPa.
Example 14—E14
The above Example 11 was repeated, but with the following changes:
The Capacitor mix is composed of:
















Carbon black (Furnace black)
50%



Active carbon (SSA 2300 m2/g)
35%



Polyester fiber
3%



Chloroplane rubber
8%



CMC
4%



Water
280%










The separator was changed to porous PE sheet without unwoven glass fiber layer and group pressure was changed to 15 kPa.
Reference Example 11—R11
The above Example 11 was repeated, but with the following changes:
No capacitor coating was applied.
Reference Example 12—R12
The above Example 11 was repeated, but with the following changes:
Group pressure was 55 kPa.
Reference Example 13—R13
The above Example 11 was repeated, but with the following changes:
Group pressure was 3 kPa.












TABLE 2








Capacity

Pb content



Sample
(Ah)
Cycle life
(%)





















E-11
42.0
75,000
12.0



E-12
38.3
80,000
14.1



E-13
43.4
65,000
11.2



E-14
44.5
55,000
9.9



R-11
40.1
25,000
6.9



R-12
32.1
80,000
7.9



R-13
44.0
11,000
4.8










In the case of R-12, Ah capacity was reduced while cycle life was high. In the case of R-13 short life was due to detachment of the capacitor layer.
Many modifications may be made to the embodiments and examples described above without departing from the spirit and scope of the invention.

## Claims

1. A lead-acid battery comprising:
at least one negative electrode comprising lead-based battery electrode material and at least one region of capacitor material overlying the lead-based battery electrode material, each electrode being in electrical connection to an outer terminal of the battery, and
at least one positive electrode which is a lead-dioxide based battery electrode without a capacitor material, each positive electrode being in electrical connection to a second outer terminal of the battery,
separator interleaving the facing electrodes
electrolyte filling at least the space of the electrodes and separators
wherein the capacitor material overlying the lead-based battery electrode material comprises 34-65% by weight of a high electrical conductivity carbonaceous material, 35-52% of a high specific surface area carbonaceous material, at least 0.1% lead and binder, and
wherein the capacitor material of each negative electrode constitutes between 1 and 15% by weight of the lead-based battery electrode material.

2. The lead-acid battery of claim 1, wherein the binder is present in an amount of between 1 and 30% by weight.

3. The lead-acid battery of claim 1, wherein the capacitor material consists of 34-65% high electrical conductivity carbonaceous material, 35-52% high specific surface area carbonaceous material, 3-40% lead, 5-20% binder and 2-10% fiber reinforcement material.

4. The lead-acid battery of claim 1, wherein a layer of capacitor material overlies all surface areas of the lead-based battery electrode material that face a positive electrode.

5. The lead-acid battery of claim 1, wherein the negative electrodes each comprise a current collector, which is coated on both faces with lead-based battery electrode material, and a layer of capacitor material overlying each face of lead-based battery electrode material that is opposite to a positive electrode.

6. The lead-acid battery of claim 1, wherein the capacitor material overlying the lead-based battery electrode material has a porosity of between 50-90%.

7. The lead-acid battery of claim 1, wherein the electrolyte is composed of sulfuric acid aqueous solution containing 0.01-0.3 mol/L of aluminum or 5-50 g/L of Al2(SO4)3.18H2O.

8. The lead-acid battery of claim 1, which is a valve regulated lead acid battery.

9. The lead-acid battery of claim 8, further comprising absorptive glass microfibre or absorbed glass mat separators between adjacent electrodes.

10. The lead-acid battery of claim 8, wherein the battery has a pressure on the electrodes of between 20 and 100 kPa.

11. The lead-acid battery of claim 8, which is operable at between 95-50% SoC.

12. The lead-acid battery of claim 1, which is a flooded electrolyte lead-acid battery.

13. The lead-acid battery of claim 12, wherein the battery has a pressure on the electrodes of between 5 and 45 kPa.

14. The lead-acid battery of claim 12, wherein the separators are interleaving the facing electrodes porous polymer separators.

15. The lead-acid battery of claim 14, wherein the porous polymer separators further comprise unwoven fibrous material reinforcement.

16. The lead-acid battery of claim 12, which is operable at between 98-80% SoC.

17. An automobile comprising a lead-acid battery of claim 12, an internal combustion engine and an alternator.

18. A lead-acid battery comprising:
at least one negative electrode comprising lead-based battery electrode material and at least one region of capacitor material overlying the lead-based battery electrode material, each electrode being in electrical connection to an outer terminal of the battery, and
at least one positive lead-dioxide based battery electrode without a capacitor material, each positive electrode being in electrical connection to a second outer terminal of the battery,
separator interleaving the facing electrodes
electrolyte filling at least the space of the electrodes and separators
wherein the capacitor material overlying the lead-based battery electrode material comprises 34-65% by weight of a high electrical conductivity carbonaceous material, 35-52% of a high specific surface area carbonaceous material, at least 0.1% lead and binder, and a polymeric fiber reinforcement material in an amount up to 10% by weight, and
wherein the capacitor material of each negative electrode constitutes between 1 and 15% by weight of the lead-based battery electrode material.

19. A lead-acid battery comprising:
at least one negative electrode comprising lead-based battery electrode material and at least one region of capacitor material overlying the lead-based battery electrode material, each electrode being in electrical connection to an outer terminal of the battery, and
at least one positive lead-dioxide based battery electrode without a capacitor material, each positive electrode being in electrical connection to a second outer terminal of the battery,
separator interleaving the facing electrodes
electrolyte filling at least the space of the electrodes and separators
wherein the capacitor material overlying the lead-based battery electrode material comprises 34-65% by weight of a high electrical conductivity carbonaceous material, 35-52% of a high specific surface area carbonaceous material, at least 0.1% lead and binder, and a non-conductive polymeric fiber reinforcement material in an amount up to 10% by weight, and
wherein the capacitor material of each negative electrode constitutes between 1 and 15% by weight of the lead-based battery electrode material.

20. The lead-acid battery of claim 1, wherein the capacitor material of each negative electrode constitutes between 5 and 10% by weight of the lead-based battery electrode material.

21. The lead-acid battery of claim 1, wherein the positive electrode comprises a positive current collector, formed from a lead alloy comprising 0.005-0.15% by weight Ba, 0.03-0.08% by weight Ca, 0.4-2.2% by weight Sn, and lead.

22. The lead-acid battery of claim 18, wherein the capacitor material of each negative electrode constitutes between 5 and 10% by weight of the lead-based battery electrode material.

23. The lead-acid battery of claim 19, wherein the capacitor material of each negative electrode constitutes between 5 and 10% by weight of the lead-based battery electrode material.

24. The lead-acid battery of claim 19, wherein the positive electrode comprises a positive current collector, formed from a lead alloy comprising 0.005-0.15% by weight Ba, 0.03-0.08% by weight Ca, 0.4-2.2% by weight Sn, and lead.

25. The lead-acid battery of claim 21, wherein lead constitutes the balance of the lead alloy.