Lead-acid battery and manufacturing method

Abstract

Lead acid batteries or battery cells, electrodes and bipolar plates for lead acid batteries or battery cells, and methods of making lead acid batteries or battery cells are provided. A lead acid battery includes a positive electrode and / or a negative electrode having a specific pore diameter distribution. The pore diameter distribution may include: a ratio of a volume of pores having a pore diameter greater than 20 [mu] m to a total pore volume of at least 15%; or a volume of pores having a pore diameter greater than 20 [mu] m of at least 0.020 ml / g.

Description

Technical Field

[0001] The present invention relates to lead-acid batteries or cells, electrodes and bipolar plates for lead-acid batteries or cells, and methods of manufacturing lead-acid batteries or cells. Background Art

[0002] The decarbonization of power generation is expected to expand the market for batteries. An important factor in the competitiveness of battery solutions is the cost of discharged electricity, which is referred to as the levelized cost of storage (LCoS). The LCoS of a battery is essentially the net present value (NPV) of all costs associated with the installation and operation of the battery (e.g., battery, control equipment, power conversion equipment, housing, cables, etc.) divided by the lifetime energy (kWh) discharged from the battery.

[0003] Lead-acid batteries (LABs) have many advantages over other storage technologies (such as lithium-ion batteries) in that they are recyclable, generally safe and are essentially low-cost batteries to produce. However, due to the lower energy throughput during the life of the battery, lead-acid batteries have a higher (and therefore less attractive) LCoS metric than lithium-ion batteries. A typical absorbed glass mat (AGM) lead-acid battery can achieve 200-500 capacity cycles before reaching the end of its life, while lithium-ion can achieve, say, 2,000 capacity cycles. A battery is generally considered to have reached the end of its life when the battery is no longer able to meet the design requirements of the application. For energy storage system (ESS) applications, the end of battery life for lead-acid batteries is generally expressed as having been reached when the discharged capacity is a certain fraction (e.g., 50%) of its initial capacity.

[0004] ESS batteries are typically valve-regulated lead-acid (VRLA) batteries. In VRLA batteries, the electrolyte is fixed (as opposed to flooded batteries) to reduce electrolyte stratification, which can degrade the battery and reduce battery life. There are two types of fixed electrolyte VLRAs: AGM batteries and gel batteries.

[0005] AGM batteries include an absorbent glass mat as a separator disposed between the positive and negative electrodes. The glass mat includes a network of glass fibers of varying sizes, typically about 1 to about 4 mm in length and about 0.5 to about 3 μm in diameter, with diameters typically less than about 1 μm. The mixture of different fiber sizes is intended to balance the competing requirements of electrolyte entrainment, fabric compressibility and incompressibility, and packing capacity. Due to the high surface tension between the electrolyte and the fibers, the fibers entrain the electrolyte, thereby immobilizing it. Battery manufacturers target a separator saturation level that is high, but not completely saturated, to provide a buffer for the O generated at the positive electrode. 2The gas provides a channel for the gas to diffuse through the separator and recombine into water at the negative electrode. This reduces the water loss of the battery and increases the turnover capacity of the battery.

[0006] Gel batteries include a gelling agent such as SiO 2 The nanopowder, which forms a gel that holds the electrolyte, helps prevent, for example, delamination or electrolyte spillage (if the battery is tilted on its side), and acts as a separator. The very fine cracks that form in the gel are 2 Diffusion provides a path for the gas. Gel batteries typically achieve significantly higher cycle capacities than AGM batteries. While AGM batteries can achieve 200-500 100% Depth of Discharge (DoD) cycles, Gel batteries can achieve 1,500 cycles. However, there are some disadvantages to gel batteries. One is that the high internal resistance of the gel separator means that gel batteries are only suitable for certain niche applications.

[0007] An important failure mode of VRLA batteries is a phenomenon known as "drying out". Drying out occurs when the saturation level of the separator decreases. This occurs due to unavoidable side reactions that occur during the feed-hydrolysis process. Although the O formed during the hydrolysis 2 Usually recombine at the negative electrode, but any H 2 Together with the stoichiometric amount of O 2 together with the loss from the battery (due to very low H 2 to water conversion), which means that water is slowly lost from the battery.

[0008] There is a need for lead acid batteries with increased capacity turnover and / or reduced water loss. It is an object of the present invention to satisfy this need in some way; and / or at least provide the public with a useful choice.

[0009] In this specification where reference has been made to patent specifications, other external documents or other sources of information, this is generally to provide a context for discussing the features of the invention. Unless expressly stated otherwise, reference to such external documents should not be construed as an admission that such documents or such sources of information are prior art or form part of the common general knowledge in the art in any area of ​​rights. Summary of the invention

[0010] In one aspect, the invention broadly resides in a lead acid battery or cell, wherein the battery or cell is a non-gel lead acid battery or cell or an absorbent glass mat (AGM) lead acid battery or cell, comprising:

[0011] a positive electrode comprising a positive active material (PAM);

[0012] a negative electrode comprising a negative active material (NAM); and

[0013] a separator capable of fixing an electrolyte disposed between the positive electrode and the negative electrode,

[0014] The positive electrode and the negative electrode each have a pore diameter distribution measured by mercury porosimetry,

[0015] The pore diameter distribution of the positive electrode and / or the negative electrode comprises that the ratio of the volume of pores having a pore diameter greater than 20 μm to the total pore volume is at least 15%.

[0016] In another aspect, the invention broadly resides in a lead-acid battery or cell, wherein the battery or cell is a non-gel lead-acid battery or cell or an absorbent glass mat (AGM) lead-acid battery or cell, comprising:

[0017] a positive electrode comprising a positive active material (PAM);

[0018] a negative electrode comprising a negative active material (NAM); and

[0019] a separator capable of fixing an electrolyte disposed between the positive electrode and the negative electrode,

[0020] The positive electrode and the negative electrode each have a pore diameter distribution measured by mercury porosimetry,

[0021] The pore diameter distribution of the positive electrode and / or the negative electrode comprises at least 0.020 ml / g of the volume of pores having a pore diameter greater than 20 μm.

[0022] In another aspect, the invention broadly resides in a lead-acid battery or cell, wherein the battery or cell is a non-gel lead-acid battery or cell or an absorbent glass mat (AGM) lead-acid battery or cell, comprising:

[0023] a positive electrode comprising a positive active material (PAM);

[0024] a negative electrode comprising a negative active material (NAM); and

[0025] a separator capable of fixing an electrolyte disposed between the positive electrode and the negative electrode,

[0026] The positive electrode and the negative electrode each have a pore diameter distribution measured by mercury porosimetry,

[0027] The pore diameter distribution of the positive electrode and / or the negative electrode includes:

[0028] (a) the ratio of the volume of pores having a pore diameter greater than 10 μm to the total pore volume is at least 50%, 55%, 60%, 65% or 70%;

[0029] (b) the ratio of the volume of pores having a pore diameter greater than 15 μm to the total pore volume is at least 25%, 30%, 35%, 40%, 45%, 50% or 55%;

[0030] (c) the ratio of the volume of pores having a pore diameter greater than 20 μm to the total pore volume is at least 15%, 20%, 25%, 30%, 40% or 45%;

[0031] (d) the ratio of the volume of pores with a pore diameter greater than 25 μm to the total pore volume is at least 15%, 20%, 25% or 30%;

[0032] (e) the ratio of the volume of pores having a pore diameter greater than 30 μm to the total pore volume is at least 10%, 15%, 20% or 25%;

[0033] (f) the ratio of the volume of pores having a pore diameter greater than 35 μm to the total pore volume is at least 10%, 15% or 20%; or

[0034] (g) Any combination of two or more of (a) to (f).

[0035] In another aspect, the invention broadly resides in a lead-acid battery or cell, wherein the battery or cell is a non-gel lead-acid battery or cell or an absorbent glass mat (AGM) lead-acid battery or cell, comprising:

[0036] a positive electrode comprising a positive active material (PAM);

[0037] a negative electrode comprising a negative active material (NAM); and

[0038] a separator capable of fixing an electrolyte disposed between the positive electrode and the negative electrode,

[0039] The positive electrode and the negative electrode each have a pore diameter distribution measured by mercury porosimetry,

[0040] The pore diameter distribution of the positive electrode and / or the negative electrode includes:

[0041] (a) the volume of pores with a pore diameter greater than 10 μm is at least 0.070, 0.075, 0.080, 0.085, 0.090, 0.095, 0.100, 0.110 or 0.120 ml / g;

[0042] (b) the volume of pores with a pore diameter greater than 15 μm is at least 0.035, 0.040, 0.050, 0.060, 0.070, 0.080, 0.090 or 0.095 ml / g;

[0043] (c) a volume of pores with a pore diameter greater than 20 μm of at least 0.020, 0.025, 0.030, 0.035, 0.040, 0.045, 0.050, 0.055, 0.060, 0.065, 0.070, 0.075, 0.080, 0.085, 0.090, 0.095, or 0.100 ml / g;

[0044] (d) the volume of pores with a pore diameter greater than 25 μm is at least 0.015, 0.020, 0.025, 0.030, 0.035, 0.040 or 0.050 ml / g;

[0045] (e) the volume of pores with a pore diameter greater than 30 μm is at least 0.015, 0.020, 0.025, 0.030, 0.035, 0.040 ml / g;

[0046] (f) the volume of pores with a pore diameter greater than 35 μm is at least 0.010, 0.015, 0.020, 0.025 or 0.030 ml / g; or

[0047] (g) Any combination of two or more of (a) to (f).

[0048] In some embodiments of the above aspects, the battery or battery cell is a non-gel lead acid battery or battery cell. In some embodiments of the above aspects, the battery or battery cell is an absorbent glass mat (AGM) lead acid battery or battery cell.

[0049] In another aspect, the invention broadly resides in a non-gel lead acid battery or cell comprising:

[0050] a positive electrode comprising a positive active material (PAM);

[0051] a negative electrode comprising a negative active material (NAM); and

[0052] a separator capable of fixing an electrolyte disposed between the positive electrode and the negative electrode,

[0053] The positive electrode and the negative electrode each have a pore diameter distribution measured by mercury porosimetry, and the separator has a pore diameter distribution measured by capillary flow porometry,

[0054] The pore diameter distribution of the positive electrode and / or the negative electrode comprises that the ratio of the volume of pores having a pore diameter greater than 10 μm to the total pore volume is at least 50%.

[0055] In another aspect, the invention broadly resides in a non-gel lead acid battery or cell comprising:

[0056] a positive electrode comprising a positive active material (PAM);

[0057] a negative electrode comprising a negative active material (NAM); and

[0058] a separator capable of fixing an electrolyte disposed between the positive electrode and the negative electrode,

[0059] The positive electrode and the negative electrode each have a pore diameter distribution measured by mercury porosimetry, and the separator has a pore diameter distribution measured by capillary flow porometry,

[0060] The pore diameter distribution of the positive electrode and / or the negative electrode includes:

[0061] (a) the ratio of the volume of pores having a pore diameter greater than 2 μm to the total pore volume is at least 85%;

[0062] (b) the ratio of the volume of pores having a pore diameter greater than 3 μm to the total pore volume is at least 80%;

[0063] (c) the ratio of the volume of pores having a pore diameter greater than 4 μm to the total pore volume is at least 75%;

[0064] (d) the ratio of the volume of pores having a pore diameter greater than 5 μm to the total pore volume is at least 75%;

[0065] (e) the ratio of the volume of pores having a pore diameter greater than 6 μm to the total pore volume is at least 70%;

[0066] (f) the ratio of the volume of pores having a pore diameter greater than 7 μm to the total pore volume is at least 70%;

[0067] (g) the ratio of the volume of pores with a pore diameter greater than 8 μm to the total pore volume is at least 65%;

[0068] (h) the ratio of the volume of pores having a pore diameter greater than 9 μm to the total pore volume is at least 55%;

[0069] (i) the ratio of the volume of pores having a pore diameter greater than 10 μm to the total pore volume is at least 50%; or

[0070] (j) Any combination of two or more of (a) to (i).

[0071] In another aspect, the invention broadly resides in a non-gel lead acid battery or cell comprising:

[0072] a positive electrode comprising a positive active material (PAM);

[0073] a negative electrode comprising a negative active material (NAM); and

[0074] a separator capable of fixing an electrolyte disposed between the positive electrode and the negative electrode,

[0075] The positive electrode and the negative electrode each have a pore diameter distribution measured by mercury porosimetry, and the separator has a pore diameter distribution measured by capillary flow porometry,

[0076] The pore diameter distribution of the positive electrode and / or the negative electrode comprises a ratio of the volume of pores having pore diameters greater than the mode pore diameter of the separator disposed between the electrodes to the total pore volume of at least 80%.

[0077] In another aspect, the invention broadly resides in an absorbent glass mat (AGM) lead acid battery or cell comprising:

[0078] a positive electrode comprising a positive active material (PAM);

[0079] a negative electrode comprising a negative active material (NAM); and

[0080] A separator capable of securing an electrolyte disposed between a positive electrode and a negative electrode, the separator comprising, consisting essentially of, or consisting of an absorbent glass fiber mat,

[0081] The positive electrode and the negative electrode each have a pore diameter distribution measured by mercury porosimetry, and the separator has a pore diameter distribution measured by capillary flow porometry,

[0082] The pore diameter distribution of the positive electrode and / or the negative electrode comprises that the ratio of the volume of pores having a pore diameter greater than 10 μm to the total pore volume is at least 50%.

[0083] In another aspect, the invention broadly resides in an absorbent glass mat (AGM) lead acid battery or cell comprising:

[0084] a positive electrode comprising a positive active material (PAM);

[0085] a negative electrode comprising a negative active material (NAM); and

[0086] A separator capable of securing an electrolyte disposed between a positive electrode and a negative electrode, the separator comprising, consisting essentially of, or consisting of an absorbent glass fiber mat,

[0087] The positive electrode and the negative electrode each have a pore diameter distribution measured by mercury porosimetry, and the separator has a pore diameter distribution measured by capillary flow porometry,

[0088] The pore diameter distribution of the positive electrode and / or the negative electrode includes:

[0089] (a) the ratio of the volume of pores having a pore diameter greater than 2 μm to the total pore volume is at least 85%;

[0090] (b) the ratio of the volume of pores having a pore diameter greater than 3 μm to the total pore volume is at least 80%;

[0091] (c) the ratio of the volume of pores having a pore diameter greater than 4 μm to the total pore volume is at least 75%;

[0092] (d) the ratio of the volume of pores having a pore diameter greater than 5 μm to the total pore volume is at least 75%;

[0093] (e) the ratio of the volume of pores having a pore diameter greater than 6 μm to the total pore volume is at least 70%;

[0094] (f) the ratio of the volume of pores having a pore diameter greater than 7 μm to the total pore volume is at least 70%;

[0095] (g) the ratio of the volume of pores with a pore diameter greater than 8 μm to the total pore volume is at least 65%;

[0096] (h) the ratio of the volume of pores having a pore diameter greater than 9 μm to the total pore volume is at least 55%;

[0097] (i) the ratio of the volume of pores having a pore diameter greater than 10 μm to the total pore volume is at least 50%; or

[0098] (j) Any combination of two or more of (a) to (i).

[0099] In another aspect, the invention broadly resides in an absorbent glass mat (AGM) lead acid battery or cell comprising:

[0100] a positive electrode comprising a positive active material (PAM);

[0101] a negative electrode comprising a negative active material (NAM); and

[0102] A separator capable of securing an electrolyte disposed between a positive electrode and a negative electrode, the separator comprising, consisting essentially of, or consisting of an absorbent glass fiber mat,

[0103] The positive electrode and the negative electrode each have a pore diameter distribution measured by mercury porosimetry, and the separator has a pore diameter distribution measured by capillary flow porometry,

[0104] The pore diameter distribution of the positive electrode and / or the negative electrode comprises a ratio of the volume of pores having pore diameters greater than the mode pore diameter of the separator disposed between the electrodes to the total pore volume of at least 80%.

[0105] In another aspect, the invention broadly resides in an absorbent glass mat (AGM) lead acid battery or cell comprising:

[0106] a positive electrode comprising a positive active material (PAM);

[0107] a negative electrode comprising a negative active material (NAM); and

[0108] a separator disposed between the positive electrode and the negative electrode, the separator comprising, consisting essentially of, or consisting of an absorbent glass fiber mat,

[0109] The positive electrode and the negative electrode each have a pore diameter distribution measured by mercury porosimetry, and the separator has a pore diameter distribution measured by capillary flow porometry,

[0110] The pore diameter distribution of the positive electrode and / or the negative electrode comprises that the ratio of the volume of pores having a pore diameter greater than 10 μm to the total pore volume is at least 50%.

[0111] In another aspect, the invention broadly resides in an absorbent glass mat (AGM) lead acid battery or cell comprising:

[0112] a positive electrode comprising a positive active material (PAM);

[0113] a negative electrode comprising a negative active material (NAM); and

[0114] a separator disposed between the positive electrode and the negative electrode, the separator comprising, consisting essentially of, or consisting of an absorbent glass fiber mat,

[0115] The positive electrode and the negative electrode each have a pore diameter distribution measured by mercury porosimetry, and the separator has a pore diameter distribution measured by capillary flow porometry,

[0116] The pore diameter distribution of the positive electrode and / or the negative electrode includes:

[0117] (a) the ratio of the volume of pores having a pore diameter greater than 2 μm to the total pore volume is at least 85% or 90%;

[0118] (b) the ratio of the volume of pores having a pore diameter greater than 3 μm to the total pore volume is at least 80% or 85%;

[0119] (c) the ratio of the volume of pores having a pore diameter greater than 4 μm to the total pore volume is at least 75%, 80% or 85%;

[0120] (d) the ratio of the volume of pores having a pore diameter greater than 5 μm to the total pore volume is at least 75%, 80% or 85%;

[0121] (e) the ratio of the volume of pores having a pore diameter greater than 6 μm to the total pore volume is at least 70%, 75% or 80%;

[0122] (f) the ratio of the volume of pores having a pore diameter greater than 7 μm to the total pore volume is at least 70%, 75% or 80%;

[0123] (g) the ratio of the volume of pores having a pore diameter greater than 8 μm to the total pore volume is at least 65%, 70% or 75%;

[0124] (h) the ratio of the volume of pores having a pore diameter greater than 9 μm to the total pore volume is at least 55%, 60%, 65%, 70% or 75%;

[0125] (i) the ratio of the volume of pores having a pore diameter greater than 10 μm to the total pore volume is at least 50%, 55%, 60%, 65% or 70%; or

[0126] (j) Any combination of two or more of (a) to (i).

[0127] In another aspect, the invention broadly resides in an absorbent glass mat (AGM) lead acid battery or cell comprising:

[0128] a positive electrode comprising a positive active material (PAM);

[0129] a negative electrode comprising a negative active material (NAM); and

[0130] a separator disposed between the positive electrode and the negative electrode, the separator comprising, consisting essentially of, or consisting of an absorbent glass fiber mat,

[0131] The positive electrode and the negative electrode each have a pore diameter distribution measured by mercury porosimetry, and the separator has a pore diameter distribution measured by capillary flow porometry,

[0132] The pore diameter distribution of the positive electrode and / or the negative electrode comprises a ratio of the volume of pores having pore diameters greater than the mode pore diameter of the separator disposed between the electrodes to the total pore volume of at least 80%.

[0133] The following embodiments and preferences may be relevant to any of the above aspects alone or in any combination of any two or more.

[0134] In various embodiments, if not already stated or otherwise stated, the battery or cell is a VRLA battery or cell.

[0135] In various embodiments, if not already stated or otherwise stated, the battery or battery cell is an absorbent glass mat (AGM) battery, wherein the separator comprises, consists essentially of, or consists of an absorbent glass fiber mat.

[0136] In various embodiments, the battery is a bipolar lead-acid battery.

[0137] In various embodiments, the battery is a bipolar lead-acid battery comprising:

[0138] One or more bipolar plates, each bipolar plate comprising

[0139] Conductive substrate,

[0140] A positive electrode comprising a positive active material (PAM), and

[0141] a negative electrode comprising a negative active material (NAM),

[0142] wherein the positive electrode is located on a first surface of the conductive substrate, and the negative electrode is located on a second surface of the conductive substrate opposite to the first surface;

[0143] a positive terminal comprising a positive electrode optionally comprising a positive active material (PAM);

[0144] a negative terminal comprising a negative electrode optionally comprising a negative active material (NAM); and

[0145] a separator disposed between each of the negative electrode and the positive electrode;

[0146] The positive electrode and the negative electrode each have a pore diameter distribution measured by mercury porosimetry, and the separators each have a pore diameter distribution measured by capillary flow porometry,

[0147] Wherein the battery comprises at least one battery cell, wherein the pore diameter distribution of the positive electrode and / or the negative electrode is as defined in any one of the above aspects.

[0148] In various embodiments, a bipolar lead-acid battery includes at least one battery cell, wherein the pore diameter distribution as defined in any of the above aspects is the pore diameter distribution of a positive electrode of a bipolar plate and / or a negative electrode of a bipolar plate.

[0149] In various embodiments, a bipolar battery includes two or more bipolar plates. In various embodiments, a bipolar battery includes a stack of bipolar plates.

[0150] In various embodiments, if not already stated or otherwise stated, the separator has a pore diameter distribution as measured by capillary flow porometry, wherein the pore diameter distribution of the positive and / or negative electrode comprises a ratio of pore volume greater than the mode pore diameter of the separator to the total pore volume of at least 80% or 85%.

[0151] In various embodiments, the separator has a pore diameter distribution measured by capillary flow porometry, wherein the pore diameter distribution of the positive and / or negative electrode comprises at least 85% of the volume of pores greater than the mode pore diameter of the separator to the total pore volume.

[0152] In various embodiments, the membrane has a pore diameter distribution measured by capillary flow porometry, wherein the membrane has a mode pore diameter of less than or equal to about 20 μm, 18 μm, 16 μm, 15 μm, 14 μm, 13 μm, 12 μm, 11 μm, or 10 μm. In certain embodiments, the membrane has a mode pore diameter of less than or equal to about 10 μm, such as less than or equal to 9 μm, 8 μm, 7 μm, 6 μm, or 5 μm. In certain embodiments, the membrane has a mode pore diameter of less than or equal to about 5 μm, such as less than or equal to 4 μm, 3 μm, 2 μm, or 1 μm.

[0153] In various embodiments, the membrane has a pore diameter distribution as measured by capillary flow porometry, wherein the membrane has about 1 to 20 μm, 1 to 18 μm, 1 to 16 μm, 1 to 15 μm, 1 to 14 μm, 1 to 13 μm, 1 to 12 μm, 1 to 11 μm, 1 to 10 μm, 1 to 9 μm, 1 to 8 μm, 1 to 7 μm, 1 to 6 μm, 1 to 5 μm, 2 to 20 μm, 2 to 18 μm, 2 to 16 μm, 2 to 15 μm, 2 to 14 μm, 2 to 13 μm, 2 to 12 μm, 2 to 11 μm, 2 to 10 μm, 2 to 9 μm, 2 to 8 μm, 2 to 7 μm, 2 to 6 μm, 2 to 5 μm, 3 to 20 μm, 3 to 18 μm, 3 to 16 μm, 3 to 15 μm, m, 3 to 14 μm, 3 to 13 μm, 3 to 12 μm, 3 to 11 μm, 3 to 10 μm, 3 to 9 μm, 3 to 8 μm, 3 to 7 μm, 3 to 6 μm, 3 to 5 μm, 4 to 20 μm, 4 to 18 μm, 4 to 16 μm, 4 to 15 μm, 4 to 14 μm, 4 to 13 μm, 4 to 12 μm, 4 to 11 μm, 4 to 1 In some embodiments, the diaphragm has a mode pore diameter of about 1 to 10 μm, such as 2 to 10 μm or 4 to 6 μm.

[0154] In various embodiments, the positive electrode and / or the negative electrode is formed from a slurry having a viscosity of about 1.5 to 5.5 g / cm 3In various embodiments, the positive electrode and / or the negative electrode is formed from a slurry having a density of about 1.5 to 5 g / cm 3 density.

[0155] In various embodiments, at least the negative electrode comprises the pore diameter distribution.

[0156] In another aspect, the invention broadly resides in an electrode for a lead-acid battery or cell, comprising an active material and having a pore diameter distribution measured by mercury porosimetry, wherein the pore diameter distribution comprises a ratio of the volume of pores having a pore diameter greater than 20 μm to at least 15% of the total pore volume.

[0157] In another aspect, the invention broadly resides in an electrode for a lead-acid battery or battery cell, comprising an active material and having a pore diameter distribution measured by mercury porosimetry, wherein the pore diameter distribution of the positive and / or negative electrode includes a volume of pores having a pore diameter greater than 20 μm of at least 0.020 ml / g.

[0158] In another aspect, the invention broadly resides in an electrode for a lead-acid battery or cell, comprising an active material and having a pore diameter distribution as measured by mercury porosimetry, wherein the pore diameter distribution comprises:

[0159] (a) the ratio of the volume of pores having a pore diameter greater than 10 μm to the total pore volume is at least 50%, 55%, 60%, 65% or 70%;

[0160] (b) the ratio of the volume of pores having a pore diameter greater than 15 μm to the total pore volume is at least 25%, 30%, 35%, 40%, 45%, 50% or 55%;

[0161] (c) the ratio of the volume of pores having a pore diameter greater than 20 μm to the total pore volume is at least 15%, 20%, 25%, 30%, 40% or 45%;

[0162] (d) the ratio of the volume of pores with a pore diameter greater than 25 μm to the total pore volume is at least 15%, 20%, 25% or 30%;

[0163] (e) the ratio of the volume of pores having a pore diameter greater than 30 μm to the total pore volume is at least 10%, 15%, 20% or 25%;

[0164] (f) the ratio of the volume of pores having a pore diameter greater than 35 μm to the total pore volume is at least 10%, 15% or 20%; or

[0165] (g) Any combination of two or more of (a) to (f).

[0166] In another aspect, the invention broadly resides in an electrode for a lead-acid battery or cell, comprising an active material and having a pore diameter distribution as measured by mercury porosimetry, wherein the pore diameter distribution comprises:

[0167] (a) the volume of pores with a pore diameter greater than 10 μm is at least 0.070, 0.075, 0.080, 0.085, 0.090, 0.095, 0.100, 0.110 or 0.120 ml / g;

[0168] (b) the volume of pores with a pore diameter greater than 15 μm is at least 0.035, 0.040, 0.050, 0.060, 0.070, 0.080, 0.090 or 0.095 ml / g;

[0169] (c) a volume of pores with a pore diameter greater than 20 μm of at least 0.020, 0.025, 0.030, 0.035, 0.040, 0.045, 0.050, 0.055, 0.060, 0.065, 0.070, 0.075, 0.080, 0.085, 0.090, 0.095, or 0.100 ml / g;

[0170] (d) the volume of pores with a pore diameter greater than 25 μm is at least 0.015, 0.020, 0.025, 0.030, 0.035, 0.040 or 0.050 ml / g;

[0171] (e) the volume of pores with a pore diameter greater than 30 μm is at least 0.015, 0.020, 0.025, 0.030, 0.035, 0.040 ml / g;

[0172] (f) the volume of pores with a pore diameter greater than 35 μm is at least 0.010, 0.015, 0.020, 0.025 or 0.030 ml / g; or

[0173] (g) Any combination of two or more of (a) to (f).

[0174] In another aspect, the invention broadly resides in an electrode for a lead-acid battery or cell, comprising an active material and having a pore diameter distribution measured by mercury porosimetry, wherein the pore diameter distribution comprises a ratio of the volume of pores having a pore diameter greater than 10 μm to at least 50% of the total pore volume.

[0175] In various embodiments, the electrode is a cathode.

[0176] In various embodiments, the electrode is composed of a material having a density of about 1.5 to 5.5 g / cm 3In various embodiments, the electrode is formed from a slurry having a density of about 1.5 to 5 g / cm 3 of slurry is formed.

[0177] In another aspect, the invention broadly resides in an electrode for a lead-acid battery or cell, comprising an active material and having a pore diameter distribution as measured by mercury porosimetry, wherein the pore diameter distribution comprises:

[0178] (a) the ratio of the volume of pores having a pore diameter greater than 2 μm to the total pore volume is at least 85%;

[0179] (b) the ratio of the volume of pores having a pore diameter greater than 3 μm to the total pore volume is at least 80%;

[0180] (c) the ratio of the volume of pores having a pore diameter greater than 4 μm to the total pore volume is at least 75%;

[0181] (d) the ratio of the volume of pores having a pore diameter greater than 5 μm to the total pore volume is at least 75%;

[0182] (e) the ratio of the volume of pores having a pore diameter greater than 6 μm to the total pore volume is at least 70%;

[0183] (f) the ratio of the volume of pores having a pore diameter greater than 7 μm to the total pore volume is at least 70%;

[0184] (g) the ratio of the volume of pores with a pore diameter greater than 8 μm to the total pore volume is at least 65%;

[0185] (h) the ratio of the volume of pores having a pore diameter greater than 9 μm to the total pore volume is at least 55%;

[0186] (i) the ratio of the volume of pores having a pore diameter greater than 10 μm to the total pore volume is at least 50%; or

[0187] (j) Any combination of two or more of (a) to (i).

[0188] In various embodiments, the electrode is a cathode.

[0189] In various embodiments, the electrode is composed of a material having a density of about 1.5 to 5.5 g / cm 3 In various embodiments, the electrode is formed from a slurry having a density of about 1.5 to 5 g / cm 3 of slurry is formed.

[0190] The following embodiments and preferences may be relevant to any of the above aspects alone or in any combination of any two or more.

[0191] In various embodiments, the pore diameter distribution includes:

[0192] (a) the ratio of the volume of pores having a pore diameter greater than 10 μm to the total pore volume is at least 50%, 55%, 60%, 65% or 70%;

[0193] (b) the ratio of the volume of pores having a pore diameter greater than 20 μm to the total pore volume is at least 15%, 20%, 25%, 30%, 40% or 45%; and

[0194] (c) the ratio of the volume of pores having a pore diameter greater than 30 μm to the total pore volume is at least 10%, 15%, 20% or 25%;

[0195] In various embodiments, the pore diameter distribution includes:

[0196] (a) the ratio of the volume of pores having a pore diameter greater than 20 μm to the total pore volume is at least 15%, 20%, 25%, 30%, 40% or 45%; and

[0197] (b) the ratio of the volume of pores having a pore diameter greater than 30 μm to the total pore volume is at least 10%, 15%, 20% or 25%;

[0198] In various embodiments, the pore diameter distribution includes:

[0199] (a) the ratio of the volume of pores having a pore diameter greater than 20 μm to the total pore volume is at least 15%, 20%, 25%, 30%, 40% or 45%;

[0200] (b) the ratio of the volume of pores having a pore diameter greater than 25 μm to the total pore volume is at least 15%, 20%, 25% or 30%; and

[0201] (c) the ratio of the volume of pores having a pore diameter greater than 30 μm to the total pore volume is at least 10%, 15%, 20% or 25%;

[0202] In various embodiments, the pore diameter distribution includes:

[0203] (a) the volume of pores with a pore diameter greater than 10 μm is at least 0.070, 0.075, 0.080, 0.085, 0.090, 0.095, 0.100, 0.110 or 0.120 ml / g;

[0204] (b) the volume of pores with pore diameters greater than 20 μm is at least 0.020, 0.025, 0.030, 0.035, 0.040, 0.045, 0.050, 0.055, 0.060, 0.065, 0.070, 0.075, 0.080, 0.085, 0.090, 0.095, or 0.100 ml / g; and

[0205] (c) the volume of pores with a pore diameter greater than 30 μm is at least 0.015, 0.020, 0.025, 0.030, 0.035, 0.040 ml / g.

[0206] In various embodiments, the pore diameter distribution includes:

[0207] (a) the volume of pores with a pore diameter greater than 20 μm is at least 0.020, 0.025, 0.030, 0.035, 0.040, 0.045, 0.050, 0.055, 0.060, 0.065, 0.070, 0.075, 0.080, 0.085, 0.090, 0.095 or 0.100 ml / g; and

[0208] (b) the volume of pores with a pore diameter greater than 30 μm is at least 0.015, 0.020, 0.025, 0.030, 0.035, 0.040 ml / g.

[0209] In various embodiments, the pore diameter distribution includes:

[0210] (a) the volume of pores with a pore diameter greater than 20 μm is at least 0.020, 0.025, 0.030, 0.035, 0.040, 0.045, 0.050, 0.055, 0.060, 0.065, 0.070, 0.075, 0.080, 0.085, 0.090, 0.095 or 0.100 ml / g;

[0211] (b) the volume of pores with a pore diameter greater than 25 μm is at least 0.015, 0.020, 0.025, 0.030, 0.035, 0.040 or 0.050 ml / g; and

[0212] (c) the volume of pores with a pore diameter greater than 30 μm is at least 0.015, 0.020, 0.025, 0.030, 0.035, 0.040 ml / g.

[0213] In various embodiments, if not already specified or otherwise specified, the pore diameter distribution of the electrode or positive electrode and / or negative electrode includes a ratio of the volume of pores with a pore diameter greater than 20 μm to the total pore volume of at least 15%, 20%, 25%, 30%, 40%, or 45%. In various embodiments, the pore diameter distribution of the electrode or positive electrode and / or negative electrode includes a ratio of the volume of pores with a pore diameter greater than 20 μm to the total pore volume of at least 20%, 25%, 30%, 40%, or 45%. In various embodiments, the pore diameter distribution of the electrode or positive electrode and / or negative electrode includes a ratio of the volume of pores with a pore diameter greater than 20 μm to the total pore volume of at least 30%, 40%, or 45%.

[0214] In various embodiments, the pore diameter distribution of the electrode or the positive and / or negative electrode includes at least 0.020, 0.025, 0.030, 0.035, 0.040, 0.045, 0.050, 0.055, 0.060, 0.065, 0.070, 0.075, 0.080, 0.085, 0.090, 0.095, or 0.100 ml / g of pore volume having a pore diameter greater than 20 μm. In various embodiments, the pore diameter distribution of the electrode or positive electrode and / or negative electrode includes at least 0.030, 0.035, 0.040, 0.045, 0.050, 0.055, 0.060, 0.065, 0.070, 0.075, 0.080, 0.085, 0.090, 0.095, or 0.100 ml / g of pores with a pore diameter greater than 20 μm. In various embodiments, the pore diameter distribution of the electrode or positive electrode and / or negative electrode includes at least 0.040, 0.045, 0.050, 0.055, 0.060, 0.065, 0.070, 0.075, 0.080, 0.085, 0.090, 0.095, or 0.100 ml / g of pores with a pore diameter greater than 20 μm.

[0215] In various embodiments, the pore diameter distribution of the electrode or positive and / or negative electrode comprises a total pore volume of at least about 0.135, 0.140, 0.145, 0.150, 0.155, 0.160, 0.165, 0.170, 0.175, 0.180, 0.185, 0.190, 0.195, or 0.200 ml / g. In various embodiments, the pore diameter distribution of the electrode or positive and / or negative electrode comprises a total pore volume of at least about 0.150, 0.155, 0.160, 0.165, 0.170, 0.175, 0.180, 0.185, 0.190, 0.195, or 0.200 ml / g.

[0216] In various embodiments, the electrode or positive electrode and / or negative electrode having the pore diameter distribution is formed from a slurry having a lead oxide content of no greater than 85% or no greater than 84%.

[0217] In various embodiments, if not already specified or otherwise specified, the pore diameter distribution of the positive and / or negative electrodes of the electrodes of the present invention or the batteries or battery cells of the present invention comprises a ratio of the volume of pores having a pore diameter greater than 10 μm to the total pore volume of at least 25%, for example at least 50%, 55%, 60%, 65% or 70%.

[0218] In various embodiments, the pore diameter distribution of the electrode or positive electrode and / or negative electrode includes at least 0.070, 0.075, 0.080, 0.085, 0.090, 0.095, 0.100, 0.110, or 0.120 ml / g of pores with a pore diameter greater than 10 μm. In various embodiments, the pore diameter distribution of the electrode or positive electrode and / or negative electrode includes at least 0.070, 0.075, 0.080, 0.085, 0.090, 0.095, 0.100, 0.110, or 0.120 ml / g of pores with a pore diameter greater than 10 μm.

[0219] In various embodiments, the pore diameter distribution of the electrode or the electrode or the positive electrode and / or the negative electrode comprises a ratio of the volume of pores with a pore diameter greater than 15 μm to the total pore volume of at least 25%, 30%, 35%, 40%, 45%, 50% or 55%. In various embodiments, the pore diameter distribution of the electrode or the electrode or the positive electrode and / or the negative electrode comprises a ratio of the volume of pores with a pore diameter greater than 15 μm to the total pore volume of at least 45%, 50% or 55%.

[0220] In various embodiments, the pore diameter distribution of the electrode or positive electrode and / or negative electrode includes at least 0.035, 0.040, 0.050, 0.060, 0.070, 0.080, 0.090 or 0.095 ml / g of pores with a pore diameter greater than 15 μm. In various embodiments, the pore diameter distribution of the electrode or positive electrode and / or negative electrode includes at least 0.070, 0.080, 0.090 or 0.095 ml / g of pores with a pore diameter greater than 15 μm.

[0221] In various embodiments, the electrode or the electrode or the positive electrode and / or the negative electrode has a pore diameter distribution comprising a ratio of the volume of pores having a pore diameter greater than 25 μm to the total pore volume of at least 15%, 20%, 25%, or 30%. In various embodiments, the electrode or the electrode or the positive electrode and / or the negative electrode has a pore diameter distribution comprising a ratio of the volume of pores having a pore diameter greater than 25 μm to the total pore volume of at least 20%, 25%, or 30%.

[0222] In various embodiments, the pore diameter distribution of the electrode or positive electrode and / or negative electrode includes at least 0.015, 0.020, 0.025, 0.030, 0.035, 0.040 or 0.050 ml / g of pores with a pore diameter greater than 25 μm. In various embodiments, the pore diameter distribution of the electrode or positive electrode and / or negative electrode includes at least 0.025, 0.030, 0.035, 0.040 or 0.050 ml / g of pores with a pore diameter greater than 25 μm.

[0223] In various embodiments, the electrode or the electrode or the positive electrode and / or the negative electrode has a pore diameter distribution comprising a ratio of the volume of pores having a pore diameter greater than 30 μm to the total pore volume of at least 10%, 15%, 20%, or 25%. In various embodiments, the electrode or the electrode or the positive electrode and / or the negative electrode has a pore diameter distribution comprising a ratio of the volume of pores having a pore diameter greater than 30 μm to the total pore volume of at least 15%, 20%, or 25%.

[0224] In various embodiments, the pore diameter distribution of the electrode or positive electrode and / or negative electrode includes at least 0.015, 0.020, 0.025, 0.030, 0.035, 0.040 ml / g of pores with a pore diameter greater than 30 μm. In various embodiments, the pore diameter distribution of the electrode or positive electrode and / or negative electrode includes at least 0.020, 0.025, 0.030, 0.035, 0.040 ml / g of pores with a pore diameter greater than 30 μm.

[0225] In various embodiments, the electrode or the pore diameter distribution of the electrode or the positive and / or negative electrode comprises a ratio of the volume of pores having a pore diameter greater than 35 μm to the total pore volume of at least 10%, 15% or 20%.

[0226] In various embodiments, the pore diameter distribution of the electrode or positive electrode and / or negative electrode includes at least 0.010, 0.015, 0.020, 0.025, or 0.030 ml / g of pores with a pore diameter greater than 35 μm. In various embodiments, the pore diameter distribution of the electrode or positive electrode and / or negative electrode includes at least 0.015, 0.020, 0.025, or 0.030 ml / g of pores with a pore diameter greater than 35 μm.

[0227] In various embodiments, the pore diameter distribution of the electrode of the invention or the positive and / or negative electrode of the battery or battery cell of the invention comprises a ratio of the volume of pores with a pore diameter greater than 5 μm to the total pore volume of at least 75%, 80% or 85%: and optionally

[0228] (a) the ratio of the volume of pores having a pore diameter greater than 2 μm to the total pore volume is at least 85% or 90%;

[0229] (b) the ratio of the volume of pores having a pore diameter greater than 3 μm to the total pore volume is at least 80% or 85%;

[0230] (c) the ratio of the volume of pores having a pore diameter greater than 4 μm to the total pore volume is at least 75%, 80% or 85%;

[0231] (d) the ratio of the volume of pores with a pore diameter greater than 6 μm to the total pore volume is at least 70%, 75% or 80%;

[0232] (e) the ratio of the volume of pores having a pore diameter greater than 7 μm to the total pore volume is at least 70%, 75% or 80%;

[0233] (f) the ratio of the volume of pores having a pore diameter greater than 8 μm to the total pore volume is at least 65%, 70% or 75%;

[0234] (g) the ratio of the volume of pores having a pore diameter greater than 9 μm to the total pore volume is at least 55%, 60%, 65%, 70% or 75%;

[0235] (h) the ratio of the volume of pores having a pore diameter greater than 10 μm to the total pore volume is at least 50%, 55%, 60%, 65% or 70%; or

[0236] (i) Any combination of two or more of (a) to (h).

[0237] In various embodiments, the pore diameter distribution of the electrode of the invention or the positive electrode and / or the negative electrode of the battery or battery cell of the invention comprises a ratio of the volume of pores having a pore diameter greater than 10 μm to the total pore volume of at least 50%, 55%, 60%, 65% or 70%; and

[0238] (a) the ratio of the volume of pores having a pore diameter greater than 2 μm to the total pore volume is at least 85% or 90%;

[0239] (b) the ratio of the volume of pores having a pore diameter greater than 3 μm to the total pore volume is at least 80% or 85%;

[0240] (c) the ratio of the volume of pores having a pore diameter greater than 4 μm to the total pore volume is at least 75%, 80% or 85%;

[0241] (d) the ratio of the volume of pores having a pore diameter greater than 5 μm to the total pore volume is at least 75%, 80% or 85%;

[0242] (e) the ratio of the volume of pores having a pore diameter greater than 6 μm to the total pore volume is at least 70%, 75% or 80%;

[0243] (f) the ratio of the volume of pores having a pore diameter greater than 7 μm to the total pore volume is at least 70%, 75% or 80%;

[0244] (g) the ratio of the volume of pores having a pore diameter greater than 8 μm to the total pore volume is at least 65%, 70% or 75%;

[0245] (h) the ratio of the volume of pores having a pore diameter greater than 9 μm to the total pore volume is at least 55%, 60%, 65%, 70% or 75%; or

[0246] (i) Any combination of two or more of (a) to (h).

[0247] In various embodiments, the pore diameter distribution of the electrode of the invention or the positive and / or negative electrode of the battery or battery cell of the invention comprises a ratio of the volume of pores greater than 10 μm to the total pore volume of at least 55%, 60%, 65% or 70%. In various embodiments, the pore diameter distribution of the electrode or the electrode or the positive and / or negative electrode comprises a ratio of the volume of pores greater than 10 μm to the total pore volume of at least 65% or 70%.

[0248] In various embodiments, the pore diameter distribution of the inventive electrode or the positive and / or negative electrode of the inventive battery or cell comprises a ratio of the volume of pores having a pore diameter greater than 1 μm to the total pore volume of at least 95%.

[0249] In various embodiments, the pore diameter distribution of the inventive electrode or the inventive positive and / or negative electrode of the inventive battery or cell comprises a ratio of the volume of pores having a pore diameter greater than 2 μm to the total pore volume of at least 85% or 90%.

[0250] In various embodiments, the pore diameter distribution of the inventive electrode or the inventive positive and / or negative electrode of the inventive battery or cell comprises at least 80% or 85% of the volume of pores having a pore diameter greater than 3 μm to the total pore volume.

[0251] In various embodiments, the pore diameter distribution of the inventive electrode or the positive and / or negative electrode of the inventive battery or cell comprises a ratio of the volume of pores having a pore diameter greater than 4 μm to the total pore volume of at least 75%, 80% or 85%.

[0252] In various embodiments, the pore diameter distribution of the inventive electrode or the inventive positive and / or negative electrode of the inventive battery or battery cell comprises a ratio of the volume of pores having a pore diameter greater than 5 μm to the total pore volume of at least 75%, 80% or 85%.

[0253] In various embodiments, the pore diameter distribution of the inventive electrode or the positive and / or negative electrode of the inventive battery or battery cell comprises at least 70%, 75% or 80% of the volume of pores with a pore diameter greater than 6 μm to the total pore volume.

[0254] In various embodiments, the pore diameter distribution of the inventive electrode or the positive and / or negative electrode of the inventive battery or battery cell comprises a ratio of the volume of pores having a pore diameter greater than 7 μm to the total pore volume of at least 70%, 75% or 80%.

[0255] In various embodiments, the pore diameter distribution of the inventive electrode or the inventive positive and / or negative electrode of the inventive battery or battery cell comprises a ratio of the volume of pores having a pore diameter greater than 8 μm to the total pore volume of at least 65%, 70% or 75%.

[0256] In various embodiments, the pore diameter distribution of the positive and / or negative electrode of the electrode of the present invention or the battery or battery cell of the present invention includes a ratio of the volume of pores with a pore diameter greater than 9 μm to the total pore volume of at least 55%, 60%, 65%, 70% or 75%.

[0257] In various embodiments, the pore diameter distribution of the electrode of the invention or the positive electrode and / or the negative electrode of the battery or battery cell of the invention comprises:

[0258] (a) the ratio of the volume of pores having a pore diameter greater than 3 μm to the total pore volume is at least 80% or 85%;

[0259] (b) the ratio of the volume of pores having a pore diameter greater than 5 μm to the total pore volume is at least 75%, 80% or 85%;

[0260] (c) the ratio of the volume of pores having a pore diameter greater than 7 μm to the total pore volume is at least 70%, 75% or 80%; and

[0261] (d) The ratio of the volume of pores having a pore diameter greater than 10 μm to the total pore volume is at least 50%, 55%, 60%, 65% or 70%.

[0262] In various embodiments, the pore diameter distribution of the electrode of the invention or the positive electrode and / or the negative electrode of the battery or battery cell of the invention comprises:

[0263] (a) the ratio of the volume of pores having a pore diameter greater than 3 μm to the total pore volume is at least 85%;

[0264] (b) the ratio of the volume of pores having a pore diameter greater than 5 μm to the total pore volume is at least 80% or 85%;

[0265] (c) the ratio of the volume of pores having a pore diameter greater than 7 μm to the total pore volume is at least 75% or 80%; and

[0266] (d) The ratio of the volume of pores having a pore diameter greater than 10 μm to the total pore volume is at least 55%, 60%, 65% or 70%.

[0267] In various embodiments, the pore diameter distribution of the electrode of the invention or the positive electrode and / or the negative electrode of the battery or battery cell of the invention comprises:

[0268] (a) the ratio of the volume of pores having a pore diameter greater than 5 μm to the total pore volume is at least 75%, 80% or 85%; and

[0269] (b) The ratio of the volume of pores having a pore diameter greater than 10 μm to the total pore volume is at least 50%, 55%, 60%, 65% or 70%.

[0270] In various embodiments, the pore diameter distribution of the electrode of the invention or the positive electrode and / or the negative electrode of the battery or battery cell of the invention comprises:

[0271] (a) the ratio of the volume of pores having a pore diameter greater than 5 μm to the total pore volume is at least 80% or 85%; and

[0272] (b) the ratio of the volume of pores having a pore diameter greater than 10 μm to the total pore volume is at least 55%, 60%, 65% or 70%;

[0273] In various embodiments, the pore diameter distribution of the electrode of the invention or the positive electrode and / or the negative electrode of the battery or battery cell of the invention comprises:

[0274] (a) the ratio of the volume of pores having a pore diameter greater than 5 μm to the total pore volume is at least 85%; and

[0275] (b) The ratio of the volume of pores having a pore diameter greater than 10 μm to the total pore volume is at least 60%, 65% or 70%.

[0276] In various embodiments, the pore diameter distribution of the electrode of the invention or the positive electrode and / or the negative electrode of the battery or battery cell of the invention comprises:

[0277] (a) the ratio of the volume of pores having a pore diameter greater than 5 μm to the total pore volume is at least 85%; and

[0278] (b) The ratio of the volume of pores having a pore diameter greater than 10 μm to the total pore volume is at least 65% or 70%.

[0279] In various embodiments, the pore diameter distribution of the positive and / or negative electrodes of the electrodes of the invention or the batteries or cells of the invention comprises: (a) a ratio of the volume of pores having a pore diameter greater than 5 μm to the total pore volume of at least 75%, 80% or 85%; and

[0280] (b) The ratio of the volume of pores having a pore diameter greater than 10 μm to the total pore volume is at least 50%, 55%, 60%, 65% or 70%.

[0281] In various embodiments, the pore diameter distribution of the positive and / or negative electrode of the electrode of the present invention or the battery or battery cell of the present invention comprises: (a) the ratio of the volume of pores with a pore diameter greater than 5 μm to the total pore volume is at least 80% or 85%; and

[0282] (b) the ratio of the volume of pores having a pore diameter greater than 10 μm to the total pore volume is at least 55%, 60%, 65% or 70%;

[0283] In various embodiments, the pore diameter distribution of the positive and / or negative electrode of the electrode of the present invention or the battery or battery cell of the present invention comprises: (a) the ratio of the volume of pores with a pore diameter greater than 5 μm to the total pore volume is at least 85%; and

[0284] (b) The ratio of the volume of pores having a pore diameter greater than 10 μm to the total pore volume is at least 60%, 65% or 70%.

[0285] In various embodiments, the pore diameter distribution of the positive electrode and / or negative electrode of the electrode of the present invention or the battery or battery cell of the present invention comprises: (a) the ratio of the volume of pores with a pore diameter greater than 3 μm to the total pore volume is at least 80% or 85%;

[0286] (b) the ratio of the volume of pores having a pore diameter greater than 5 μm to the total pore volume is at least 75%, 80% or 85%;

[0287] (c) the ratio of the volume of pores having a pore diameter greater than 7 μm to the total pore volume is at least 70%, 75% or 80%; and

[0288] (d) The ratio of the volume of pores having a pore diameter greater than 10 μm to the total pore volume is at least 50%, 55%, 60%, 65% or 70%.

[0289] In various embodiments, the pore diameter distribution of the positive electrode and / or negative electrode of the electrode of the present invention or the battery or battery cell of the present invention comprises: (a) a ratio of the volume of pores having a pore diameter greater than 3 μm to the total pore volume of at least 85%;

[0290] (b) the ratio of the volume of pores having a pore diameter greater than 5 μm to the total pore volume is at least 80% or 85%;

[0291] (c) the ratio of the volume of pores having a pore diameter greater than 7 μm to the total pore volume is at least 75% or 80%; and

[0292] (d) The ratio of the volume of pores having a pore diameter greater than 10 μm to the total pore volume is at least 55%, 60%, 65% or 70%.

[0293] In various embodiments, the pore diameter distribution of the positive electrode and / or negative electrode of the electrode of the present invention or the battery or battery cell of the present invention comprises: (a) the ratio of the volume of pores with a pore diameter greater than 3 μm to the total pore volume is at least 80% or 85%;

[0294] (b) the ratio of the volume of pores having a pore diameter greater than 5 μm to the total pore volume is at least 75%, 80% or 85%;

[0295] (c) the ratio of the volume of pores having a pore diameter greater than 10 μm to the total pore volume is at least 50%, 55%, 60%, 65% or 70%.

[0296] In various embodiments, the pore diameter distribution of the positive electrode and / or negative electrode of the electrode of the present invention or the battery or battery cell of the present invention comprises: (a) a ratio of the volume of pores having a pore diameter greater than 3 μm to the total pore volume of at least 85%;

[0297] (b) the ratio of the volume of pores having a pore diameter greater than 5 μm to the total pore volume is at least 80% or 85%;

[0298] (c) the ratio of the volume of pores having a pore diameter greater than 10 μm to the total pore volume is at least 55%, 60%, 65% or 70%;

[0299] In various embodiments, the pore diameter distribution of the positive electrode and / or negative electrode of the electrode of the present invention or the battery or battery cell of the present invention comprises: (a) a ratio of the volume of pores having a pore diameter greater than 3 μm to the total pore volume of at least 85%;

[0300] (b) the ratio of the volume of pores having a pore diameter greater than 5 μm to the total pore volume is at least 85%;

[0301] (c) The ratio of the volume of pores having a pore diameter greater than 10 μm to the total pore volume is at least 60%, 65% or 70%.

[0302] In various embodiments, the pore diameter distribution of the electrode of the invention or the positive electrode and / or the negative electrode of the battery or battery cell of the invention comprises:

[0303] (a) the ratio of the volume of pores having a pore diameter greater than 3 μm to the total pore volume is at least 85%;

[0304] (b) the ratio of the volume of pores having a pore diameter greater than 5 μm to the total pore volume is at least 85%;

[0305] (c) The ratio of the volume of pores having a pore diameter greater than 10 μm to the total pore volume is at least 65% or 70%.

[0306] In another aspect, the invention broadly resides in a bipolar plate for a bipolar lead-acid battery comprising:

[0307] Conductive substrate,

[0308] A positive electrode comprising a positive active material (PAM), and

[0309] a negative electrode comprising a negative active material (NAM),

[0310] wherein the positive electrode is located on a first surface of the conductive substrate, and the negative electrode is located on a second surface of the conductive substrate opposite to the first surface; and

[0311] The positive electrode and / or the negative electrode is an electrode of the present invention.

[0312] The following embodiments and preferences may be relevant to any of the above aspects alone or in any combination of any two or more.

[0313] In various embodiments, the positive electrode and / or the negative electrode includes an electrode frame in which the active material is disposed.

[0314] In various embodiments, the electrode frame comprises a fiber material.

[0315] In various embodiments, the fibrous material has an average inter-fiber spacing of less than about 250 μm.

[0316] In various embodiments, the fiber material has a thickness of about 0.05 g / cm 3 Up to 0.2g / cm 3 , 0.07g / cm 3 Up to 0.17g / cm 3 , or 0.08g / cm 3 Up to 0.15g / cm 3 The bulk density.

[0317] In another aspect, the present invention broadly resides in a method of making a lead-acid battery or battery cell of the present invention, the method comprising:

[0318] Providing a positive electrode including a positive electrode active material oxide (PAM oxide) slurry, a negative electrode including a negative electrode active material oxide (NAM oxide) slurry, and a separator capable of fixing an electrolyte;

[0319] Assembling a battery or battery cell from a positive electrode, a negative electrode and a separator;

[0320] adding electrolytes; and

[0321] The battery or cell is subjected to an initial cell or battery charge to form a cell.

[0322] In various embodiments, providing at least one positive electrode and / or at least one negative electrode includes applying a positive active material oxide (PAM oxide) slurry or a negative active material oxide (NAM oxide) slurry to an electrode frame.

[0323] In various embodiments, the slurry is applied to the electrode frame within a defined slurry coating area.

[0324] In various embodiments, the slurry at the time of impregnation has a viscosity of about 1.5 to 5.5 g / cm 3 In various embodiments, the slurry during impregnation has a density of about 1.5 to 5 g / cm 3 density.

[0325] In another aspect, the invention broadly resides in a method of making an electrode of the invention, the method comprising applying a positive active material oxide (PAM oxide) slurry or a negative active material oxide (NAM oxide) slurry to an electrode frame.

[0326] In various embodiments, the slurry is applied to the electrode frame within a defined slurry coating area.

[0327] In various embodiments, the slurry at the time of impregnation has a viscosity of about 1.5 to 5.5 g / cm 3 In various embodiments, the slurry during impregnation has a density of about 1.5 to 5 g / cm 3 density.

[0328] In another aspect, the invention resides primarily in a method of making a bipolar plate of the invention, the method comprising providing an electrode of the invention on a first surface of a conductive substrate and providing an electrode of opposite polarity on a second surface of the conductive substrate opposite the first surface.

[0329] definition

[0330] The term "comprising" means "consisting at least in part of..." When interpreting each expression containing the term "comprising" in this specification, features other than the term or those beginning with the term may also exist. Related terms such as "comprise" and "comprises" are to be interpreted in the same way.

[0331] The term "non-gel lead-acid battery or battery cell" and similar terms such as "non-gel lead-acid battery" refer to a lead-acid battery or battery cell that includes an electrolyte that is not fixed in a gel. In some embodiments, the non-gel lead-acid battery or battery cell does not include a gelling agent. In other embodiments, the non-gel lead-acid battery or battery cell includes a gelling agent in the electrolyte in an amount insufficient to produce a gel capable of fixing the electrolyte. In some embodiments, the non-gel lead-acid battery or battery cell includes a portion of the electrolyte fixed in the gel and a portion of the electrolyte that is not fixed in the gel. For example, in some embodiments, the non-gel lead-acid battery or battery cell includes a gelled top cover layer. In such an embodiment, preferably, most of the electrolyte of the battery or battery cell (e.g., at least 50%, 60%, 70%, 80%, 90%, 95% or 100%) is not fixed in the gel.

[0332] The singular forms "a," "an," and "the" include plural referents unless otherwise indicated.

[0333] As used herein, the term "and / or" means "and" or "or", or both.

[0334] As used herein, "(s)" following a noun is intended to refer to the plural and / or singular forms of that noun.

[0335] Unless otherwise indicated, all percentages, parts, ratios, etc. are by weight.

[0336] Unless otherwise indicated, the term "negative electrode active material" (or "NAM") as used herein refers to the non-lattice lead active material in and / or on the negative electrode in a formed and fully charged (100% SOC) state.

[0337] Unless otherwise indicated, as used herein, the term "positive electrode active material" (or "PAM") refers to the lead dioxide active material in a formed and fully charged (100% SOC) state within and / or on the positive electrode.

[0338] Unless otherwise specified, the term "negative active material oxide" (or "NAM oxide") used herein refers to a dry lead oxide slurry from which the negative active material is formed. During the formation of the NAM, PbO in the lead oxide of the NAM oxide is converted to Pb.

[0339] Unless otherwise specified, as used herein, the term "positive active material oxide" (or "PAM oxide") refers to a dry lead-containing oxide slurry that forms a positive active material. During the formation of the PAM, the PbO in the lead-containing oxide of the NAM oxide is converted to PbO 2 .

[0340] Unless otherwise indicated, as used herein, the term "dried unformed state" (or "DUF") refers to the state of the paste material mass in the electrode after drying and optionally also after any curing to a moisture content of about 1% or less.

[0341] The term "fully charged" as used herein (and similar terms such as "fully charged state", etc.) refers to the state of a battery or cell or an electrode of a battery or cell at 100% state of charge (SoC). A battery or cell or an electrode of a battery or cell may be in a fully charged state after charging with a minimum duration of 24 hours at 2.667 V / cell for a flooded battery or 2.467 V / cell for an AGM battery.

[0342] Numerical ranges disclosed herein (e.g., 1 to 10) also include reference to all rational numbers within that range (e.g., 1, 1.1, 2, 3, 3.9, 4, 5, 6, 6.5, 7, 8, 9, and 10) as well as any range of rational numbers within that range (e.g., 2 to 8, 1.5 to 5.5, and 3.1 to 4.7), and thus, all subranges of all ranges explicitly disclosed herein are hereby explicitly disclosed. These are merely examples of what is specifically intended, and all possible combinations of numerical values ​​between the lowest and highest values ​​recited are considered to be expressly stated in this application in a similar manner.

[0343] The present invention may also be broadly described as including the parts, elements and features referred to or indicated in the specification of the present application, either individually or collectively, and any or all combinations of any two or more of said parts, elements or features, and where specific integers are referred to herein, these specific integers have known equivalents in the art to which the present invention relates, and these known equivalents are deemed to be incorporated herein as if individually set forth.

[0344] Although the present invention is broadly defined above, it will be appreciated by those skilled in the art that the present invention is not limited thereto and that the present invention also includes embodiments for which the following description gives examples. BRIEF DESCRIPTION OF THE DRAWINGS

[0345] The present invention is further described by way of example with reference to the accompanying drawings, in which:

[0346] Figure 1 is a graph of the ratio (fraction) of the cumulative intrusion volume (in ml / g) to the pore diameter (in μm) of the negative electrodes of the present invention formed from slurries having a lead oxide (LO) content of 77, 80, 83 and 86% from batteries B6129, B6135, B6141 and B6123, respectively, and the conventional negative electrodes from batteries B6191, B6193, B6195 and B6197, respectively, as shown in Example 2. The curve shows that the electrode of the present invention has a greater proportion of pores with pore diameters of 10 to 90 μm and 20 to 90 μm than the conventional electrode.

[0347] Figure 2is a graph of the cumulative intrusion volume (in ml / g) versus pore diameter (in μm) for negative electrodes of the invention formed from slurries having lead oxide (LO) contents of 77, 80, 83, and 86% from cells B6129, B6135, B6141, and B6123, respectively, and conventional negative electrodes from cells B6191, B6193, B6195, and B6197, respectively, as shown in Example 2. The graph shows that the electrodes of the invention have a volume of pores having pore diameters of 10 to 90 μm and a volume of pores having pore diameters of 20 to 90 μm that are greater than the volume of pores in these pore diameter ranges for the conventional electrodes. The graph also shows that the electrodes of the invention formed from slurries having lead oxide contents of 77%, 80%, and 83% have a greater maximum intrusion volume (total pore volume) than the conventional electrodes.

[0348] Figure 3 is a graph of flow rate (in l / min) versus pressure (in bar) for dry (Dry Data) and wet (Wet Data) membrane samples measured using the capillary flow porometry method as described in Example 3.

[0349] Figure 4 is a plot of cumulative pore flow (in %) versus pore diameter (in μm) (Cumulative Flow %) and differential flow (in %) versus pore diameter (in μm) (Differential Flow %), showing the use of Figure 3 The data shown in are obtained for the pore diameter distribution of the separator.

[0350] Figure 5 is the performance of a battery using the electrode of the present invention, and

[0351] Figure 6 A schematic diagram showing a defined sizing zone implemented to impregnate a textile material with sizing is shown. DETAILED DESCRIPTION

[0352] The present invention broadly includes a lead-acid battery or battery cell, which includes a positive electrode, a negative electrode and a separator disposed between the electrodes. The electrodes and the separator are porous, each having a pore diameter distribution. The pore diameter distribution of the electrode is measured by mercury porosimetry. The pore diameter distribution of the separator is measured by capillary flow porosimetry.

[0353] As used herein, the term "pore diameter distribution measured by mercury porosimetry" and similar terms, such as "pore diameter distribution measured by mercury porosimetry" refer to the pore diameter distribution measured by mercury porosimetry according to ISO 15901-1:2016 standard. Electrode samples for mercury porosimetry analysis were prepared according to the method described in Example 2. In certain embodiments, the samples were prepared after electrical pretreatment of the battery as described in Example 2. The analysis should be performed by an ISO certified laboratory.

[0354] Unless otherwise indicated, the pore diameter distribution as measured by mercury porosimetry as referred to herein is for pores having a pore diameter of 90 μm or less. Pores having a pore diameter greater than 90 μm are not included in the mercury porosimetry analysis. For example, in the case of a volume of pores having a pore diameter greater than a stated value (e.g., 10, 15, 20, 30, or 35 μm), it is understood that the volume is the volume of pores having a pore diameter greater than the stated value up to (but not exceeding) 90 μm. Similarly, when the total pore volume (or maximum intrusion volume) is indicated herein relative to a pore diameter distribution measured by mercury porosimetry, it will be understood that the volume is the volume of pores having a pore diameter of 90 μm or less.

[0355] Unless otherwise specified, the pore size distribution as measured by capillary flow porometry referred to herein is pores having a pore diameter of 100 μm or less. Pores having a pore diameter greater than 100 μm are not included in the capillary flow porometry analysis.

[0356] In some embodiments, the pore diameter distribution of the positive and / or negative electrode includes a ratio of the volume of pores with a pore diameter greater than 20 μm to the total pore volume of at least 15%. In other embodiments, the pore diameter distribution of the positive and / or negative electrode includes a volume of pores with a pore diameter greater than 20 μm of at least 0.020 ml / g. In some embodiments, the pore diameter distribution of the positive and / or negative electrode includes a ratio of the volume of pores with a pore diameter greater than 10 μm to the total pore volume of at least 50%. In other embodiments, the pore diameter distribution of the positive and / or negative electrode includes a ratio of the volume of pores with a pore diameter greater than the mode pore diameter of the separator disposed between the electrodes to the total pore volume of at least 80%. In other embodiments, the pore diameter distribution of the positive electrode and / or the negative electrode includes: (a) the ratio of the volume of pores with a pore diameter greater than 2 μm to the total pore volume is at least 85%; (b) the ratio of the volume of pores with a pore diameter greater than 3 μm to the total pore volume is at least 80%; (c) the ratio of the volume of pores with a pore diameter greater than 4 μm to the total pore volume is at least 75%; (d) the ratio of the volume of pores with a pore diameter greater than 5 μm to the total pore volume is at least 75%; (e) the ratio of the volume of pores with a pore diameter greater than 6 μm to the total pore volume is at least 10%. (f) the ratio of the volume of pores with a pore diameter greater than 7 μm to the total pore volume is at least 70%; (g) the ratio of the volume of pores with a pore diameter greater than 8 μm to the total pore volume is at least 65%; (h) the ratio of the volume of pores with a pore diameter greater than 9 μm to the total pore volume is at least 55%; (i) the ratio of the volume of pores with a pore diameter greater than 10 μm to the total pore volume is at least 50%; or (j) any combination of two or more of (a) to (i). In other embodiments, the pore diameter distribution of the positive electrode and / or the negative electrode is as defined above in any of the other aspects of the battery or battery cell of the present invention. The volume of pores, total pore volume and mode pore diameter are measured by mercury porosimetry of the electrode and by capillary flow porosimetry of the separator (as part of measuring the pore diameter distribution of the positive and negative electrodes and the separator). In some preferred embodiments, at least the negative electrode has the ratio.

[0357] Advantageously, such an arrangement provides optimal saturation of the electrolyte to the separator material, and can avoid or reduce the drying of the electrolyte from the separator, and / or can result in preferential drying in the negative electrode and / or positive electrode on the separator. In some embodiments, such preferential drying occurs in the negative electrode. Alternatively or additionally, such an arrangement can result in preferential drying or reduction of the electrolyte at the negative electrode and / or positive electrode rather than in the separator as in the conventional prior art battery construction. In some embodiments, such preferential drying or reduction of the electrolyte occurs in the negative electrode. Without wishing to be bound, it is believed that in certain embodiments, such an arrangement that provides optimal saturation of the separator and / or preferential drying or a reduction of the electrolyte in the positive electrode and / or negative electrode rather than the separator can result in an increase in the number of capacity turnovers compared to the conventional prior art battery construction.

[0358] The diaphragm is basically disposed between the positive electrode and the negative electrode for physically separating the electrodes and allowing the flow of current, gas and / or electrolyte therethrough. In addition, the diaphragm must also be durable enough to withstand assembly operations and to function reliably under the strong vibration and thermal stresses that it will encounter during the service life of the battery. In certain embodiments, the diaphragm may include, consist essentially of, or consist of an absorbent glass fiber mat material. For example, such a diaphragm may be readily commercially available from Hollingsworth & Vose. In some embodiments, the diaphragm has a mode pore diameter of less than or equal to about 20 μm, such as less than 15, 10, or 5 μm, or a mode pore diameter of about 1 to 20 μm, such as about 1 to 15, 2 to 10, or 4 to 8, or 4 to 5 μm. For example, in some embodiments, the diaphragm may have a mode pore diameter of 5 μm or less, such as about 4 to 5 μm.

[0359] It has been found that, at least in some embodiments, a battery comprising a separator having a mode pore diameter of about 5 μm or less and a positive and / or negative electrode having a pore diameter distribution as defined in any aspect of the battery or battery cell of the present invention above has increased capacity turnover compared to a corresponding battery using a conventional electrode configuration, the pore diameter distribution, for example, a ratio of the volume of pores with a pore diameter greater than 10 μm to the total pore volume of at least 50% or a ratio of the volume of pores with a pore diameter greater than 20 μm to the total pore volume of at least 15%. It has also been found that the negative electrode in such a battery of the present invention has a reduced electrolyte (measured in moisture) content. Without wishing to be bound, it is believed that this is consistent with drying or reduction of the electrolyte in the battery occurring preferentially in the negative electrode.

[0360] The battery or battery cell is assembled from a positive electrode and a negative electrode. The electrode can be formed by a slurry coating method as described herein and with reference to PCT International Application PCT / IB2016 / 057459 (published as WO 2017 / 098444 A1), which is incorporated herein by reference in its entirety, to obtain a suitable pore volume and pore diameter distribution. In some embodiments, the electrode may be provided with a tab. Alternatively, in other embodiments, the electrode may not be provided with a tab, for example, in the case where the electrode is used in a VRLA that does not require the same, such as a bipolar battery.

[0361] The preferred form of the slurry comprises a mixture of Pb and PbO particles with dilute sulfuric acid. Alternatively, the slurry may comprise lead sulfate (PbSO 4) particles and dilute sulfuric acid. For example, the slurry for at least the negative electrode may also optionally contain other additives, such as carbon black, barium sulfate, and / or a swelling agent such as lignin sulfonate. Examples of suitable lignin sulfonates include, but are not limited to, those available from Borregaard AS Norway and available from Vanisperse TM Name (such as Vanisperse TM A or Vanisperse TM HT-1). Barium sulfate acts as a seed for the crystallization of lead sulfate, promoting the reaction of lead to lead sulfate. If the expander is soluble in the slurry or electrolyte, the expander can be provided in the slurry or electrolyte. The expander helps prevent sulfate particles from agglomerating at the negative plate, such as forming solid blocks of lead sulfate during discharge. For example, the expander can include about 0.01wt% to 5wt%, 0.01wt% to 2.5wt%, 0.01wt% to 2wt%, 0.01wt% to 1.5wt%, 0.01wt% to 1wt%, 0.01wt% to 0.8wt% of the active material-oxide. Typically, the expander is added to the slurry at a concentration of about 0.2wt% or more of the slurry.

[0362] In various embodiments, for example, when impregnated, the slurry has a viscosity of at least 1.5 gm / cm 3 , for example at least 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9 or 3 gm / cm 3 In some embodiments, the density is at least 3.5 gm / cm 3 , or at least 4.0gm / cm 3 or 1.5 to 7 gm / cm 3 , or 3 to 6.5 gm / cm 3 , or 3 to 6 gm / cm 3 , or 3 to 5.5 gm / cm 3 In some embodiments, for example, when impregnated, the slurry has a viscosity of 1.5 to 7 g / cm 3 , more preferably 2 to 6.5 g / cm 3 , more preferably 2.5 to 6 g / cm 3 , more preferably 3 to 5 g / cm 3 ; or at least 1.5gm / cm 3 , for example at least 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9 or 3 gm / cm 3(and a useful range may be selected from any two of these values). In some embodiments, the density is at least 3.5 gm / cm 3 , or at least 4.0gm / cm 3 or 1.5 to 7 gm / cm 3 , or 3 to 6.5 gm / cm 3 , or 3 to 6 gm / cm 3 , or 3 to 5.5 gm / cm 3 , or 3 to 5 gm / cm 3 .

[0363] In some embodiments, the NAM oxide has a carbon content of at least 1.5 gm / cm 3 In some embodiments, the NAM oxide has a density of at least 3 gm / cm 3 or have a density of at least 3.5 gm / cm 3 density.

[0364] In certain embodiments, the slurry has a particle size of less than 5 g / cm 3 In certain embodiments, the slurry has a density of about 1.5 to 5 g / cm 3 In certain embodiments, the slurry has a density of about 1.5 to 5.5 g / cm 3 density.

[0365] The slurry may have a sufficiently low shear strength to flow (slump) when placed in a cylindrical shape on a horizontal surface under gravity. Sufficient slump was observed for a significant slump of a 30 mm high x 30 mm diameter cylinder when impregnated into an electrode fabric. Preferably, the slurry has a creamy consistency. It has been found that this is achieved where the slurry includes less than about 6 wt%, or less than 5 wt%, or less than 4 wt%, or less than 3 wt%, or less than 2 wt% or less than 1 wt% sulfuric acid.

[0366] In some embodiments, the slurry has a yield stress in the range of about 5 Pa to about 500 Pa and / or a plastic viscosity in the range of about 0.1 Pa.s to about 5 Pa.s.

[0367] In some embodiments, the lead oxide content and / or liquid component content of the slurry can be varied to achieve a slurry density. In some such embodiments, the lead oxide content is no greater than 88%, or no greater than 87%, or no greater than 86%, or no greater than 85%, or no greater than 84%.

[0368] In certain exemplary embodiments, the positive electrode and / or negative electrode having the pore diameter distribution is formed from a slurry having a lead oxide content of no greater than 85% or no greater than 84%. In certain embodiments, the lead oxide content is no greater than 84%.

[0369] The electrode may include an electrode frame. The electrode frame includes a network suitable for providing a structural form to the slurry and / or keeping it in the frame. In at least some embodiments, the frame is equipped with interconnected gaps and / or spaces. In at least some embodiments, the electrode frame includes foam. In at least some embodiments, the electrode frame includes a fiber material, such as a carbon fiber. In at least some other embodiments, the fiber material is a non-conductive fiber material, such as oxidized polyacrylonitrile (PAN) fiber (OPF), glass fiber, silicon carbide fiber or alumina fiber material. The fiber material can be a woven material (including crossed warp and weft fibers), a knitted material or a non-woven material, such as a fluid-entangled material (such as a hydraulically entangled material) and / or a felt material or a knitted carbon fiber material. Preferably, the fiber material has been hydraulically entangled. Preferably, the fiber material has been needle-punched. Preferably, the bulk density of the fiber material is about 0.05g / cm 3 Up to 0.2g / cm 3 , or about 0.07 to 0.17 g / cm 3 , or about 0.08 to 0.15 g / cm 3 The material generally has an average inter-fiber spacing between fibers in the fibrous material of about 1 to about 5 average fiber diameters and / or less than about 250 microns, and in some embodiments less than about 200 microns, less than about 100 microns, less than about 50 microns, less than about 20 microns, or less than about 10 microns. Alternatively, the material has an electrode per unit volume of 10 3 Up to 10 6 m 2 / m 3The amount of the cylindrical surface of the fiber. The fiber diameter can be in the range of about 1 micron to about 30 microns, about 4 microns to about 20 microns, about 5 microns to about 15 microns. In some embodiments, the average fiber diameter is less than about 20 microns. The void ratio in the (unimpregnated) material can be, for example, at least about 80% or at least about 95%, for example, to about 98%. Typically, the fiber material has a length and width dimension in the main plane of the material and an average thickness perpendicular to the main plane of the material, which can be, for example, about 0.2mm or about 1mm and / or less than 10mm or less than 5mm or less than 3mm or less than 2mm. Felt or other nonwoven planar electrode materials can be manufactured to very low thickness, such as 2.5mm. In at least some embodiments, the fiber material includes filaments with an average length in the range of 3 to 50mm. The fiber material can have a thickness (transverse to the length and width or planar dimensions of the electrode) many times smaller than the planar dimensions or any planar dimensions of the electrode, such as about 10, 20, 50 or 100 times. For example, the thickness can be less than about 10 mm, or less than about 5 mm, or less than about 3 mm, or less than about 2 mm, or about or less than about 1 mm, or about 0.2 mm. For example, each of the length and width dimensions in the plane of the electrode can be greater than about 50 mm or about 100 mm. Such an electrode has a planar form with low thickness. In a preferred form, the electrode is substantially planar and has a size of, for example, less than about 200 mm, or less than about 150 mm, or less than about 100 mm, or less than about 70 mm, or less than about 50 mm, or about 30 mm or less (with or without a macroscopic current collector) for external connection along at least one edge of the electrode for VRLA battery applications. In various embodiments, the width of the electrode is less than about 200 mm, or less than about 150 mm, or less than about 100 mm, or less than about 70 mm, or less than about 50 mm, or about 30 mm. In various embodiments, the width of the electrode is 140 mm. In larger embodiments, the length and / or width dimensions of the electrode may be up to 1.5 m, up to 1 m, or between 0.5 and 1 m, for example with or without a tab. Alternatively, this planar form may be formed, for example, as a cylindrical electrode. In some embodiments, the fiber material may be conductive. For example, the fiber material may be a metal fiber material or mesh, or a non-metal fiber material having a metal material, such as a Pb coating, coated on the fiber. In other embodiments, the fiber material may be a non-conductive fiber material. In addition to the positive active material (PAM) and / or the negative active material (NAM), the positive and / or negative electrode may include lead or lead-based materials for collecting current and / or transferring current to and from the electrode, such as a metal tab, which may include a lead alloy, preferably a lead-calcium alloy, a lead-tin alloy or a lead-aluminum alloy, or any combination of two or more thereof.The PAM, NAM, and / or lead or lead-based materials preferably contain no or low levels of antimony, as described herein.

[0370] The electrode framework, and if a fiber material is included, the fibers thereof can be flexible, which will help accommodate volume changes of the active material (PAM / NAM) attached to the fiber material during battery cycling, and the micron-sized fibers can also reinforce the active material to assist and / or maintain pore size and / or pore volume.

[0371] If a fibrous current collector material is included, the electrode frame can be mechanically supported, and the supporting mechanical frame can also provide electrical connections (external electrode connections) of each electrode to the battery cell or battery terminal. For example, one or more square or rectangular adjacent layers of fibrous current collector material can be supported by a peripheral metal frame on all sides or between opposing metal frame elements on two opposing sides to form a planar battery plate. Alternatively, for example, concentric cylindrical positive and negative plates can be supported by a circular metal frame at either cylindrical end. Typically, all forms of external connectors are referred to herein as "tabs".

[0372] The porosity of the electrode can be changed by, for example, using slurries of different densities. It has been found that, at least in some embodiments, the use of a slurry with a lower slurry density (or lead oxide content) can provide an electrode with a greater proportion of pores, the pores having, for example, a pore diameter greater than 5 μm, more particularly greater than 10 μm, or more particularly greater than 20 μm (e.g., greater than 25 μm, 30 μm, or 35 μm). As described in the Examples, the use of a slurry with a lead oxide content of 77% results in an electrode having a greater proportion of pores having a pore diameter greater than 5 μm, 10 μm, or 20 μm than an electrode prepared from a slurry with a lead oxide content of 86%. Slurry density is an important factor in the structural strength of the electrode active material. The particle-to-particle connection in the active material needs to be strong enough to withstand the charge / discharge process without causing the particles to lose contact, and to withstand the applied forces, such as vibrations, protrusions, etc., during use. Although the porosity of the electrode can be increased by reducing the slurry density (e.g., increasing the amount of water in the slurry relative to the amount of lead oxide), the structural strength of the formed active material can be reduced. Without wishing to be bound, it is believed that at least in some embodiments, the use of an electrode frame comprising a fibrous material can provide structural strength to an electrode prepared from a lower density slurry.

[0373] After mixing, the slurry is applied to the electrode frame, usually under pressure, by applying the slurry to the electrode frame or vice versa. In some such embodiments, the slurry is applied using a slurry coating machine. In at least some embodiments, the method includes applying the slurry to the electrode frame by dipping the slurry into the electrode frame under pressure. The pressure is sufficient to overcome the flow resistance of the fiber to the slurry, the frictional flow resistance of the fiber to the slurry, and the surface tension of the slurry. In some embodiments, the pressure applied to the slurry is in the pressure range of 0.2kPa to 100kPa, 0.2kPa to 80kPa, or 0.2kPa to 60kPa. In some embodiments, the slurry is subjected to ultrasonic vibrations with a frequency in the range of 5Hz to 500kHz.

[0374] In other embodiments, pressure is provided in a defined slurrying zone as part of a slurry application zone. The defined slurrying zone includes a vibrator that moves the fiber material through the defined slurrying zone, vibrates the slurry in the defined volume, and is arranged to maintain a pressure source on the vibrating slurry to impregnate the slurry into the fiber material through the main surface of the fiber material and pass it through the fiber material. The defined slurrying zone can be provided as part of a machine for impregnating the slurry into the fiber material, wherein the carbon fiber material is continuously moved through the machine, and in other embodiments, the carbon fiber material can be under tension. In a further embodiment, the machine can be arranged to compress the fiber material when the fiber material moves into and / or through the defined slurrying zone. In the absence of a machine, the same defined slurrying zone can be further provided.

[0375] In some embodiments, any variation in the mass loading of lead (or Pb equivalent) per cubic centimeter of the internal volume of the fibrous material is less than 50%, or less than 30%, or less than 20%. In other embodiments, greater than about 50%, or greater than about 65%, or greater than about 80% of the slurry (total volume) impregnated into and on one or more surfaces of the fibrous material is within the internal volume of the fibrous material.

[0376] refer to Figure 6. This schematically illustrates the impregnation of slurry into a fibrous material 4 while moving in a machine direction indicated by arrow MD. The fibers are pulled by a driven roller 12. The fibrous material 4 moves on a flat surface 1, which is, for example, a flat plate. Slurry P is delivered from a slurry supply source (not shown) to the fibrous material 4 opposite the surface 1 through a slurry delivery outlet 5, which specifically includes an orifice 6, which is at least as wide as the width of the fibrous material 4 in the machine direction. Immediately in front of the slurry delivery outlet 5 in the machine direction is a vibrator 3, which has a lower surface 8. The lower surface 8 extends through the fibrous material 4 and is angled downwardly toward the fibrous material in the machine direction as shown, but it is contemplated that the lower surface 8 can be moved within a range of motion from an angled position to a position substantially coplanar with the fibers. In front of the orifice 6, a defined slurry coating zone is defined between the underside 8 of the vibrator 3 and the surface 1. In some cases, the cross-sectional area of ​​the defined slurry coating zone in the machine direction (in Figure 6 The cross section in the figure is approximately triangular) decreases in the machine direction, as shown. However, in an optional embodiment, the defined slurry coating area has a height perpendicular to the plane of the surface 1 and the coplanar fibrous material 4.

[0377] In use, as the fibrous material 4 moves forward in the machine direction, slurry moving under pressure as indicated by arrow P is continuously delivered under pressure from the orifice 6 into a defined slurrying zone defined between the lower surface 8 of the vibrator 3 and the surface 1 therebelow, and to the left and right side walls on either side of the defined slurrying zone. The slurry is delivered under pressure, such as pumping pressure, which maintains a static pressure on the wedge-shaped body of slurry 2 held within the defined slurrying zone, which assists in impregnating the slurry into the fibrous material.

[0378] The slurry in the defined coating zone can be considered as a body of slurry flowing under pressure and can also be fluidized by vibration, where the pressure is a static pressure sufficient to overcome the flow resistance of the fibers, thereby causing the slurry to flow into and continuously impregnate the major surfaces of the fibrous material with the slurry.

[0379] In some embodiments, the porosity of an electrode including a fiber material as an electrode frame can be changed by controlling the method of impregnating the fiber material with a slurry. For example, the degree of slurry penetration into the fiber material and the final porosity of the electrode formed thereby can be controlled by changing the pressure and / or vibration applied to the slurry during the impregnation process.

[0380] After pasting, the electrode is dried, for example, by air drying or flash drying, and then cured. For example, air drying can be carried out at a temperature of less than 40°C or less than 30°C for at least 4 hours, or at least 12 hours, or at least 18 hours, or at least 24 hours. In some embodiments, drying is by flash drying. Flash drying may not expose the electrode to a temperature greater than 80°C for more than 60 seconds, or no more than 40 seconds, or no more than 30 seconds. In some embodiments, flash drying includes exposing the electrode to an elevated temperature, preferably no more than 80°C, for a short time, for example no more than 60, 40, 30, or 20 seconds. In at least some embodiments, the dried electrodes are dry to the touch and / or dry enough to be stacked on top of each other without sticking together. The flash dried electrode may have a moisture content (mass percentage of water in the flash dried slurry) of less than about 15 wt%, 14 wt%, 13 wt%, or 12 wt%, such as about 2 to 14, 3 to 14, 5 to 14, 2 to 13, 3 to 13, 5 to 13, 2 to 12, 3 to 12, 5 to 12, or 7 to 12 wt%. In some embodiments, flash drying can reduce the moisture content of the electrode to about 9%.

[0381] The dried electrode is then transferred to an oven and cured. In various embodiments, the moisture content of the electrode (the mass percentage of water in the flash dried slurry) is reduced to less than about 1wt%, for example, less than about 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3 or 0.2wt% by curing. In some embodiments, a stack of 5 or more electrodes is provided to the oven at one time. In the curing process after the electrode is transferred to the oven, the temperature of the oven is slowly increased from room temperature to at least about 50°C, for example, a temperature of 60°C, while maintaining high relative humidity, for example, at least 90°C. The oven is then maintained at this elevated temperature, while the relative humidity is slowly reduced to about less than 20%, for example, 10% relative humidity. The low relative humidity and elevated temperature are then maintained for a period of time, and then the temperature is gradually reduced to room temperature, while the relative humidity is increased to about, for example, 20%.

[0382] The electrodes are then inserted into the cell container and electrically connected as alternating positive and negative electrodes with a suitable separator between each positive and negative electrode. The electrolyte is then added to the cell. The rate of electrolyte addition can be controlled so that the cell temperature does not rise above about 60°C, or about 70°C, or about 80°C (due to exothermic reactions). Controlling the temperature can prevent or minimize the expansion agent (e.g., lignin sulfonate) from being destroyed / denatured. The electrolyte can be cooled, for example, to less than 20°C, or less than 10°C, or less than 5°C, or to about 0°C or less, or to about -10°C or less. Prior to adding the electrolyte, alternatively or additionally, the cell or battery can be cooled, for example, in a cooled water bath, for example, to less than 20°C, or less than 10°C, or less than 5°C, or to about 0°C or less, or to about -10°C or less.

[0383] After assembly, the battery or cell is then initially charged to form the cell. During initial electrode or cell formation after cell or battery construction (the first charge cycle during which active particle connections are formed), electrode or cell formation first occurs by building a conductive framework that absorbs most of the Pb in the negative active material, typically building a few millimeters in length (a connected string of perhaps a thousand or more micron-sized particles connected end to end). This stage also produces small PbSO 4 Particles. Secondly, these smaller particles are attached to the conductive framework to provide and receive current. It may be advantageous that during the formation process, the charging current is periodically pulsed.

[0384] 12V VRLA AGM batteries generally follow a standard construction process, where a 2V battery cell or plate group is constructed using electrodes with an alternative configuration of 1 negative electrode, 1 positive electrode, and a separator between them. The plate groups are then stacked together to form a stack, which can then be subjected to compression to ensure that each stack fits into the chamber of the battery housing and to ensure contact between the electrode itself and the separator. In some cases, the plunger moves over the top of the plate group to force the battery stack into each chamber. Each chamber with a stack or plate group is now a battery cell. Each battery cell is connected to the terminal of the battery using a casting tape. The lid is placed firmly on the battery housing. Then the electrolyte filling begins, where the battery is vacuumed while the electrolyte is introduced into the battery. The vacuum forces the electrolyte into the separator and the plate. The process can be repeated several times to ensure complete saturation. Then, the battery is ready for forming. This general method can be used for batteries of any alternative size, such as 48V.

[0385] The difference between a bipolar battery and a monopolar battery (e.g., a monopolar AGM battery) is that a bipolar plate replaces a chamber wall, and the electrode and / or NAM / PAM is not provided with a terminal tab. The bipolar plate is permeable to the flow of electrons through the surface of the bipolar wall, but is impermeable to the electrolyte. In all other aspects, the bipolar battery can be constructed using a construction technique similar to that used for a monopolar AGM battery. A cathode or negative electrode including NAM and an anode or positive electrode including PAM are provided on the opposite surface of a conductive substrate, thereby providing a bipolar plate or a bipolar electrode. A bipolar battery may include one bipolar plate, but typically includes a stack of bipolar plates. The battery includes a positive terminal and a negative terminal, the positive terminal including a positive electrode, the negative terminal including a negative electrode located at the opposite end of a bipolar plate or a bipolar plate stack, the positive terminal facing an electrode with opposite polarity, and a separator between the electrodes. In an embodiment in which the battery includes a bipolar plate stack, a separator is stacked between the stacks so that the electrodes with opposite polarities face each other. The battery stack is then assembled and provided and / or inserted into a battery housing. The stack is compressed to ensure that the electrodes and the separator are compressed relative to each other. The lid is placed on the housing or the housing is otherwise sealed and a vacuum is drawn as in the AGM configuration described, whereupon the electrolyte is added. Again, this electrolyte addition process may be performed several times to ensure complete saturation of the separator. The cell is then ready for forming.

[0386] In various embodiments, the batteries of the present invention meet one or more of the water consumption requirements according to the European Standard (EN5042-1:2015), as described below:

[0387] Demand Level Test temperature Duration (days) <![CDATA[Weight loss g / (Ah C 20 )]]> W1 +60℃+2℃ 21 <24 W2 +60℃+2℃ 21 <16 W3 +60℃+2℃ 42 <8 W4 +60℃+2℃ 42 <4 W5 +60℃+2℃ 84 <4

[0388] In some embodiments, the water consumption of the battery is less than 9 g / (Ah C 20 ), or less than 8g / (Ah C 20 ), or less than 7g / (Ah C 20 ), or less than 6g / (Ah C 20 ), or less than 5g / (Ah C 20 ) or less than 4g / (Ah C 20 ), or less than 3g / (AhC 20 ) or less than 2g / (Ah C 20 ).

[0389] Example

[0390] The following non-limiting examples are provided to illustrate the invention without limiting its scope in any way.

[0391] Example 1 - Preparation of electrodes and construction of a battery

[0392] This example illustrates the preparation of an electrode of the present invention and the construction of a battery using the electrode.

[0393] method

[0394] Electrode preparation

[0395] The electrode of the present invention is prepared by the following method. A lead oxide slurry containing the amount of lead oxide shown in Table 1 below is mixed with a certain amount of swelling agent dissolved in deionized water in a mixing bowl equipped with a mixer. The remaining ingredients are then added to the bowl. Mixing is started again, and the total mixing time does not exceed 15 minutes. This produces a slurry slurry that is then used to slurry a carbon fiber felt fabric equipped with a lead lug. The carbon fiber felt (available as a hydroentangled fiber from Zoltek) has a 120 to 160 gm / m 2 The pasted electrode is then quickly dried to a moisture content of 3-20% and then cured in a humidity and temperature controlled curing oven. The cured plate is then used to construct the battery of the present invention.

[0396] Table 1: Material Quantity

[0397]

[0398]

[0399] Battery structure

[0400] Batteries B6129, B6135, B6141 and B6123 of the present invention are constructed by assembling one negative electrode, two positive electrode (1N / 2P) battery cells using the negative electrode of the present invention prepared in a dry unformed state using 77%, 80%, 83% and 86% lead oxide slurry, respectively, and having a Daramic (Polyethylene battery separator) separator for traditional positive electrode.

[0401] The control batteries B6191, B6193, B6195 and B6197 were constructed by assembling a one negative electrode, two positive electrode (1N / 2P) battery cell, using conventional positive and negative electrodes in a dry, unformed state with a Daramic (Polyethylene battery separator) separator. B6191 and B6197 contain conventional negative electrodes for enhanced flooded batteries (EFB) from different manufacturers. B6193 and B6195 contain conventional negative electrodes for AGM batteries from different manufacturers.

[0402] Battery Formation

[0403] From the structural point of view, the battery cells of the control battery and the battery of the present invention are first immersed in 1.15sg sulfuric acid electrolyte for 1 hour. The battery is then connected to an Arbin BT2000 test bench, the nominal positive electrode is connected to the positive terminal, and the nominal negative terminal is connected to the negative lead of the test bench. The battery is then formed by converting the electrodes to their respective polarities by charging, wherein the lead oxide on the positive electrode is converted to PbO 2 , the lead oxide on the negative electrode is converted into Pb. The battery cell is fully charged.

[0404] Example 2 - Mercury Porosimetry Test

[0405] This example illustrates the preparation and testing of the porosity of samples by mercury intrusion porosimetry.

[0406] method

[0407] The formed cells from Example 1 were then subjected to the following electrical pre-treatment test.

[0408] Electrical pretreatment

[0409] After formation, each cell was subjected to C20 discharge (full discharge to 1.75 V / cell at 20 hour discharge rate) and then full charge for 24 hours with a current limit of 5 times the 20 hour rate and a voltage limit of 2.667 V / cell.

[0410] Disassembly and preparation of electrodes for sampling

[0411] To ensure that the battery is completely replaced before removal, charge each battery for 16 hours with a current limit of 5 times the 20-hour rate and a voltage limit of 2.667 V / cell. Remove the battery within two hours of charging completion and remove the negative terminal from the battery.

[0412] Wash the negative electrode with isopropanol immediately upon removal from the disassembled cell. Immediately expose the electrode completely to the isopropanol with the electrode oriented vertically. The volume of isopropanol is at least about 10 times the geometric volume of the exposed electrode. Place a lid on the container to prevent the ingress of atmospheric oxygen. After soaking for 2 hours, exchange the isopropanol by pouring off the free isopropanol and adding an equal volume of fresh isopropanol. After soaking for 2 hours, perform a second isopropanol exchange and then allow the electrode to soak for 16 hours. Then perform a third and final isopropanol exchange. After soaking for 2 hours, pour off the free isopropanol and place the electrode vertically in a vacuum oven.

[0413] The electrodes were dried at 40°C under vacuum (less than 10% atmosphere) for at least 4 hours until completely dry (typically providing less than 0.5% moisture content). Care was taken to strictly limit exposure of the electrodes to air throughout the disassembly, washing, and drying process, thereby minimizing oxidation of the lead (due to atmospheric oxygen). In addition, the electrode samples were not exposed to water or high humidity conditions during disassembly, washing, drying, and sampling - since exposure to water during washing and drying is known to cause oxidation and recrystallization artifacts in the lead electrodes.

[0414] Electrode sampling for mercury intrusion porosity measurements

[0415] The electrodes were subdivided into smaller samples and sealed in vacuum bags to exclude oxygen during transportation of the samples to an external laboratory accredited by the International Organization for Standardization (ISO) for mercury intrusion porosimetry testing.

[0416] The method of subdividing the sample depends on the underlying electrode frame or grid of the electrode. The electrode of the present invention utilizing carbon fiber felt fabric as the electrode frame was cut from the (horizontal) center of the electrode into samples measuring approximately 100 mm x 50 mm. Conventional electrodes utilizing a conventional lead frame grid as the electrode frame were sampled by carefully pushing the active material particles out of the center portion of the lead frame. The active material particles measured approximately 4.0 mm x 4.0 mm x 1.6 mm.

[0417] The samples are then packaged in vacuum sealed bags ready for mercury intrusion porosimetry testing. The samples are then sent to an ISO certified external laboratory. Sub-sampling of the provided samples is performed by an ISO accredited external laboratory according to their procedures. The samples are then analyzed for mercury porosimetry according to ISO 15901-1:2016 standard.

[0418] No sample conditioning was performed by the external laboratory prior to the porosimetry measurement (conditioning that would result in significant exposure to air or moisture, or exposure to temperatures above 40°C should be avoided) - the samples were tested as provided. Conventional electrode sample particles were taken directly from their vacuum packaging and placed in the penetrometer. The samples of the present invention were provided to the external laboratory in an oversized size, so individual pieces of the appropriate size were cut using a scalpel blade and placed in the penetrometer.

[0419] A MicroActive AutoPore V 9600 Version 2.03.22 instrument was used. Samples of conventional technology were measured in a 5 Bulb, 1.131 Stem, Powder penetrometer. Samples of the present invention were measured in a 5 Bulb, 0.392 Stem, Solid penetrometer. A "blank" correction was performed on each penetrometer before sample measurement. The samples were measured with the low-pressure evacuation target pressure set to 30 μmHg, achieved with an initial evacuation rate of 3.0 psia / min, and when the target pressure was reached, the evacuation continued for 5 min. A mercury filling pressure of 1.0 psi was used. A balance rate of low-pressure and high-pressure operation of 0.050 μL / g·s was used. The mercury contact angle was set to 140 degrees and the mercury surface tension was set to 485.0 dynes / cm.

[0420] The results of the analysis are listed in Tables 2 and 3 below and Figure 1 and 2 This pore volume and pore diameter distribution analysis does not include pores with diameters greater than 90 μm.

[0421] Table 2: Pore size relative to cumulative intrusion volume fraction

[0422]

[0423]

[0424] Table 3: Absolute cumulative intrusion volume relative to pore size

[0425] In the table, the "ml / g" value for any given row is the intrusion volume between 90 μm and the pore diameter specified for that row {x}. The values ​​are inclusive (ie, include the boundary values ​​of "x" and 90 μm).

[0426]

[0427] In a typical mercury porosimetry analysis, a sample is placed in a vacuum-sealed sample cup containing a certain amount of mercury, and then pressure is applied. Typically, the drag of the surface tension of the mercury acting along the line in contact with the pores creates a force that prevents mercury from entering, which is measured to determine the porosity of the sample. By measuring the volume of mercury that invades the sample when the pressure increases, the volume of pores of the corresponding pore diameter size in the sample can be determined. The pore diameter distribution is calculated using the Washburn equation. A relationship diagram of the cumulative intrusion volume and pore diameter is obtained, so that the volume of pores with a specific pore diameter and the total volume of the sample pores can be determined. A diagram of the logarithmic differential intrusion versus pore diameter is also obtained, so that the mode pore diameter of the sample can be determined. The mode pore diameter represents the pore diameter at the peak (i.e., the highest peak) of the maximum intrusion volume in the logarithmic differential diagram.

[0428] result

[0429] Table 2 shows that the fraction or ratio (as a%) of the volume of pore diameters greater than 10 μm to the total pore volume (maximum intrusion volume) is between about 80% and 85% for the 77% PbO-coated electrode and between about 60% and 65% for the 86% PbO-coated electrode, but less than 50% for each of these conventional electrodes. Similarly, the fraction or ratio (as a%) of the volume of pore diameters greater than 20 μm to the total pore volume is between about 25% and 30% for the 77% PbO-coated electrode and between about 55% and 60% for the 86% PbO-coated electrode, but less than 15% for each of these conventional electrodes. This is also Figure 1 It is shown in Figure 1 The data included in Table 2 are plotted.

[0430] Table 3 shows that for all electrodes of the present invention, the cumulative intrusion volume in the case of pore diameters of 10 μm or 20 μm is greater than that of conventional electrodes. Table 3 shows that the electrodes of the present invention have a pore volume of at least 0.020 ml / g, the pores having a pore diameter greater than 20 μm (to 90 μm). This is also Figure 2 It is shown in Figure 2 The data included in Table 3 are plotted. Figure 2 It is also shown that the 77%, 80% and 83% PbO paste electrodes have larger maximum intrusion volumes than the conventional electrodes.

[0431] Example 3 - Capillary Flow Porometry

[0432] This example illustrates the preparation of samples for capillary flow porometry (also known as liquid displacement porometry or gas-liquid displacement porometry).

[0433] method

[0434] A 25 mm diameter disc sample of the same type of separator used in the battery of the present invention from Example 1 was cut. The sample was then subjected to capillary flow porometry. The results of the analysis are given in Figure 3 and 4 Given in.

[0435] In a typical analysis performed in the field, the sample is wetted with Porofil (a liquid of known viscosity and surface tension) to fill at least all of the through-holes. The wetted sample is then sealed into a sample holder. Gas pressure (air or nitrogen) is then applied to one side of the sample. Generally, as the gas pressure is increased, the liquid empties from the largest holes to the smallest holes. The resulting gas flow is measured until all holes are emptied of liquid. The analysis is then repeated on the sample without wetting (i.e., on the sample in a dry state). This produces a wet curve and a dry curve for the sample, which plots the gas flow rate versus pressure. The wet and dry curves obtained for the fiberglass matte sample SP020 are shown in Figure 3 From these wet and dry curves, the pore diameter distribution can be calculated using the Washburn equation. Figure 3 The data shown in the figure show the pore diameter distribution of the glass fiber matte sample SP020. Figure 4 Shown in. Figure 4 The Differential Flow % graph in Figure 2 shows the mode pore diameter of the membrane.

[0436] Example 4 - Cycle Life

[0437] This example shows the improved cycle life of VRLA cells, particularly bipolar cells, using the electrodes of the present invention.

[0438] method

[0439] A bipolar cell was constructed by assembling a negative electrode having a lead oxide content of 77%, a conventional positive electrode, a conductive substrate for bipolar plates and an AGM separator made according to Example 1, and then providing to a battery housing. The cell was then subjected to the cell forming procedure described in Example 1. In its fully charged state, the cell was then transferred for deep discharge cycles according to the following procedure.

[0440] Deep discharge cycle

[0441] The test procedure includes a long-term test protocol according to the International Battery Association standard BCIS-06, in which the battery is subjected to a full 100% deep discharge and recharge cycle. Performance is measured by the number of deep discharge cycles (capacity turnover) that the battery can sustain before the battery drops below a certain level of performance (e.g., 50% of its starting performance measured in capacity (Ah)). The results of the deep discharge cycle performance of the bipolar battery in this example are shown in Figure 5 middle.

[0442] result

[0443] like Figure 5As shown, the battery has a starting capacity of 10Ah, which rises to 12Ah at about 200 cycles. The battery performance does not drop below 50% of its starting capacity until about 1750 cycles. In contrast, a typical LAB is expected to have a cycle life (life until performance drops below 50% of starting capacity) of only about 500 cycles.

[0444] Example 5 - Moisture Content

[0445] This example illustrates a negative electrode used as an electrolyte reservoir.

[0446] method

[0447] A 2V 60Ah cell (nominal capacity) was constructed using the 86% lead oxide paste electrode as described in Example 1 as the negative electrode in a 7 negative electrode, 6 positive electrode (7N / 6P) configuration. The positive electrode was a conventional positive electrode commercially available. The positive electrode was paired with the negative electrode with a glass fiber material AGM separator for automotive batteries (available from Hollingsworth & Vose) in between. A control flooded 7N / 6P cell was also constructed using conventional negative and positive electrodes and an automotive battery separator as used in Example 1 between the negative and positive electrodes.

[0448] The cells were then subjected to the cell formation procedure described in Example 1. The cells were then transferred to testing 16 hours after formation to ensure that the cells were fully charged.

[0449] Upon completion of the post-form test, the cells were transferred for DCA testing using the Ford EU (Test B) DCA test protocol. The cells were subjected to the Ford EU test for 13 weeks. After completing the DCA test, the cells were then subjected to the C20 capacity test, which is an industry standard test for low rate charge and discharge.

[0450] The cells were then disassembled into their components. Samples of electrodes and separators were cut. Each sample weighed approximately 5 g each. Care was taken not to compress the samples during the sample cutting process to ensure minimal moisture loss during the process. Additionally, for the positive electrode, care was taken to avoid including inert Pb grid / frame materials in the sample.

[0451] The samples were then placed in a moisture analyzer (AND TM ML-50 Industrial Precision Moisture Analyzer, available from Total Laboratory Systems), where the operating conditions are defined by a maximum temperature of 150°C, the measured values ​​of the samples are determined when the mass loss rate is less than 0.2% / min. The results are listed in Table 4 below.

[0452] Table 4:

[0453]

[0454] result

[0455] The negative electrode in the inventive cell had a moisture content of 4.6%, compared to the control cell where the negative electrode had a moisture content of 10%. The moisture content of the positive electrode in the inventive cell and the control cell was the same and significantly higher than the moisture content of the negative electrode in the inventive cell.

[0456] The following numbered paragraphs define specific aspects and embodiments of the invention:

[0457] 1. A lead-acid battery or cell, wherein the battery or cell is a non-gel lead-acid battery or cell or an absorbent glass mat (AGM) lead-acid battery or cell, comprising:

[0458] a positive electrode comprising a positive active material (PAM);

[0459] a negative electrode comprising a negative active material (NAM); and

[0460] a separator capable of fixing an electrolyte disposed between the positive electrode and the negative electrode,

[0461] The positive electrode and the negative electrode each have a pore diameter distribution measured by mercury porosimetry,

[0462] The pore diameter distribution of the positive electrode and / or the negative electrode comprises that the ratio of the volume of pores having a pore diameter greater than 20 μm to the total pore volume is at least 15%.

[0463] 2. A lead-acid battery or cell, wherein the battery or cell is a non-gel lead-acid battery or cell or an absorbent glass mat (AGM) lead-acid battery or cell, comprising:

[0464] a positive electrode comprising a positive active material (PAM);

[0465] a negative electrode comprising a negative active material (NAM); and

[0466] a separator capable of fixing an electrolyte disposed between the positive electrode and the negative electrode,

[0467] The positive electrode and the negative electrode each have a pore diameter distribution measured by mercury porosimetry,

[0468] The pore diameter distribution of the positive electrode and / or the negative electrode comprises at least 0.020 ml / g of the volume of pores having a pore diameter greater than 20 μm.

[0469] 3. A lead acid battery or cell, wherein the battery or cell is a non-gel lead acid battery or cell or an absorbent glass mat (AGM) lead acid battery or cell, comprising:

[0470] a positive electrode comprising a positive active material (PAM);

[0471] a negative electrode comprising a negative active material (NAM); and

[0472] a separator capable of fixing an electrolyte disposed between the positive electrode and the negative electrode,

[0473] The positive electrode and the negative electrode each have a pore diameter distribution measured by mercury porosimetry,

[0474] The pore diameter distribution of the positive electrode and / or the negative electrode includes:

[0475] (a) the ratio of the volume of pores having a pore diameter greater than 10 μm to the total pore volume is at least 50%, 55%, 60%, 65% or 70%;

[0476] (b) the ratio of the volume of pores having a pore diameter greater than 15 μm to the total pore volume is at least 25%, 30%, 35%, 40%, 45%, 50% or 55%;

[0477] (c) the ratio of the volume of pores having a pore diameter greater than 20 μm to the total pore volume is at least 15%, 20%, 25%, 30%, 40% or 45%;

[0478] (d) the ratio of the volume of pores with a pore diameter greater than 25 μm to the total pore volume is at least 15%, 20%, 25% or 30%;

[0479] (e) the ratio of the volume of pores having a pore diameter greater than 30 μm to the total pore volume is at least 10%, 15%, 20% or 25%;

[0480] (f) the ratio of the volume of pores having a pore diameter greater than 35 μm to the total pore volume is at least 10%, 15% or 20%; or

[0481] (g) Any combination of two or more of (a) to (f).

[0482] 4. A lead acid battery or cell, wherein the battery or cell is a non-gel lead acid battery or cell or an absorbent glass mat (AGM) lead acid battery or cell, comprising:

[0483] a positive electrode comprising a positive active material (PAM);

[0484] a negative electrode comprising a negative active material (NAM); and

[0485] a separator capable of fixing an electrolyte disposed between the positive electrode and the negative electrode,

[0486] The positive electrode and the negative electrode each have a pore diameter distribution measured by mercury porosimetry,

[0487] The pore diameter distribution of the positive electrode and / or the negative electrode includes:

[0488] (a) the volume of pores with a pore diameter greater than 10 μm is at least 0.070, 0.075, 0.080, 0.085, 0.090, 0.095, 0.100, 0.110 or 0.120 ml / g;

[0489] (b) the volume of pores with a pore diameter greater than 15 μm is at least 0.035, 0.040, 0.050, 0.060, 0.070, 0.080, 0.090 or 0.095 ml / g;

[0490] (c) a volume of pores with a pore diameter greater than 20 μm of at least 0.020, 0.025, 0.030, 0.035, 0.040, 0.045, 0.050, 0.055, 0.060, 0.065, 0.070, 0.075, 0.080, 0.085, 0.090, 0.095, or 0.100 ml / g;

[0491] (d) the volume of pores with a pore diameter greater than 25 μm is at least 0.015, 0.020, 0.025, 0.030, 0.035, 0.040 or 0.050 ml / g;

[0492] (e) the volume of pores with a pore diameter greater than 30 μm is at least 0.015, 0.020, 0.025, 0.030, 0.035, 0.040 ml / g;

[0493] (f) the volume of pores with a pore diameter greater than 35 μm is at least 0.010, 0.015, 0.020, 0.025 or 0.030 ml / g; or

[0494] (g) Any combination of two or more of (a) to (f).

[0495] 5. A lead acid battery or cell according to any one of the preceding paragraphs, wherein the battery or cell is a non-gel lead acid battery or cell.

[0496] 6. A lead-acid battery or cell according to any one of the preceding paragraphs, wherein the battery or cell is an absorbent glass mat (AGM) lead-acid battery or cell.

[0497] 7. A non-gel lead-acid battery or battery cell comprising:

[0498] a positive electrode comprising a positive active material (PAM);

[0499] a negative electrode comprising a negative active material (NAM); and

[0500] a separator capable of fixing an electrolyte disposed between the positive electrode and the negative electrode,

[0501] The positive electrode and the negative electrode each have a pore diameter distribution measured by mercury porosimetry, and the separator has a pore diameter distribution measured by capillary flow porometry,

[0502] The pore diameter distribution of the positive electrode and / or the negative electrode comprises that the ratio of the volume of pores having a pore diameter greater than 10 μm to the total pore volume is at least 50%.

[0503] 8. A non-gel lead-acid battery or battery cell comprising:

[0504] a positive electrode comprising a positive active material (PAM);

[0505] a negative electrode comprising a negative active material (NAM); and

[0506] a separator capable of fixing an electrolyte disposed between the positive electrode and the negative electrode,

[0507] The positive electrode and the negative electrode each have a pore diameter distribution measured by mercury porosimetry, and the separator has a pore diameter distribution measured by capillary flow porometry,

[0508] The pore diameter distribution of the positive electrode and / or the negative electrode includes:

[0509] (a) the ratio of the volume of pores having a pore diameter greater than 2 μm to the total pore volume is at least 85%;

[0510] (b) the ratio of the volume of pores having a pore diameter greater than 3 μm to the total pore volume is at least 80%;

[0511] (c) the ratio of the volume of pores having a pore diameter greater than 4 μm to the total pore volume is at least 75%;

[0512] (d) the ratio of the volume of pores having a pore diameter greater than 5 μm to the total pore volume is at least 75%;

[0513] (e) the ratio of the volume of pores having a pore diameter greater than 6 μm to the total pore volume is at least 70%;

[0514] (f) the ratio of the volume of pores having a pore diameter greater than 7 μm to the total pore volume is at least 70%;

[0515] (g) the ratio of the volume of pores with a pore diameter greater than 8 μm to the total pore volume is at least 65%;

[0516] (h) the ratio of the volume of pores having a pore diameter greater than 9 μm to the total pore volume is at least 55%;

[0517] (i) the ratio of the volume of pores having a pore diameter greater than 10 μm to the total pore volume is at least 50%; or

[0518] (j) Any combination of two or more of (a) to (i).

[0519] 9. A non-gel lead-acid battery or battery cell comprising:

[0520] a positive electrode comprising a positive active material (PAM);

[0521] a negative electrode comprising a negative active material (NAM); and

[0522] a separator capable of fixing an electrolyte disposed between the positive electrode and the negative electrode,

[0523] The positive electrode and the negative electrode each have a pore diameter distribution measured by mercury porosimetry, and the separator has a pore diameter distribution measured by capillary flow porometry,

[0524] The pore diameter distribution of the positive electrode and / or the negative electrode comprises a ratio of the volume of pores having pore diameters greater than the mode pore diameter of the separator disposed between the electrodes to the total pore volume of at least 80%.

[0525] 10. An absorbent glass mat (AGM) lead acid battery or battery cell comprising:

[0526] a positive electrode comprising a positive active material (PAM);

[0527] a negative electrode comprising a negative active material (NAM); and

[0528] A separator capable of securing an electrolyte disposed between a positive electrode and a negative electrode, the separator comprising, consisting essentially of, or consisting of an absorbent glass fiber mat,

[0529] The positive electrode and the negative electrode each have a pore diameter distribution measured by mercury porosimetry, and the separator has a pore diameter distribution measured by capillary flow porometry,

[0530] The pore diameter distribution of the positive electrode and / or the negative electrode comprises that the ratio of the volume of pores having a pore diameter greater than 10 μm to the total pore volume is at least 50%.

[0531] 11. An absorbent glass mat (AGM) lead acid battery or cell comprising:

[0532] a positive electrode comprising a positive active material (PAM);

[0533] a negative electrode comprising a negative active material (NAM); and

[0534] A separator capable of securing an electrolyte disposed between a positive electrode and a negative electrode, the separator comprising, consisting essentially of, or consisting of an absorbent glass fiber mat,

[0535] The positive electrode and the negative electrode each have a pore diameter distribution measured by mercury porosimetry, and the separator has a pore diameter distribution measured by capillary flow porometry,

[0536] The pore diameter distribution of the positive electrode and / or the negative electrode includes:

[0537] (a) the ratio of the volume of pores having a pore diameter greater than 2 μm to the total pore volume is at least 85%;

[0538] (b) the ratio of the volume of pores having a pore diameter greater than 3 μm to the total pore volume is at least 80%;

[0539] (c) the ratio of the volume of pores having a pore diameter greater than 4 μm to the total pore volume is at least 75%;

[0540] (d) the ratio of the volume of pores having a pore diameter greater than 5 μm to the total pore volume is at least 75%;

[0541] (e) the ratio of the volume of pores having a pore diameter greater than 6 μm to the total pore volume is at least 70%;

[0542] (f) the ratio of the volume of pores having a pore diameter greater than 7 μm to the total pore volume is at least 70%;

[0543] (g) the ratio of the volume of pores with a pore diameter greater than 8 μm to the total pore volume is at least 65%;

[0544] (h) the ratio of the volume of pores having a pore diameter greater than 9 μm to the total pore volume is at least 55%;

[0545] (i) the ratio of the volume of pores having a pore diameter greater than 10 μm to the total pore volume is at least 50%; or

[0546] (j) Any combination of two or more of (a) to (i).

[0547] 12. An absorbent glass mat (AGM) lead acid battery or cell comprising:

[0548] a positive electrode comprising a positive active material (PAM);

[0549] a negative electrode comprising a negative active material (NAM); and

[0550] A separator capable of securing an electrolyte disposed between a positive electrode and a negative electrode, the separator comprising, consisting essentially of, or consisting of an absorbent glass fiber mat,

[0551] The positive electrode and the negative electrode each have a pore diameter distribution measured by mercury porosimetry, and the separator has a pore diameter distribution measured by capillary flow porometry,

[0552] The pore diameter distribution of the positive electrode and / or the negative electrode comprises a ratio of the volume of pores having pore diameters greater than the mode pore diameter of the separator disposed between the electrodes to the total pore volume of at least 80%.

[0553] 13. The lead-acid battery or cell of any of the preceding paragraphs, wherein the negative electrode has the pore diameter distribution, or both the negative electrode and the positive electrode have the pore diameter distribution.

[0554] 14. A lead acid battery or cell according to any one of the preceding paragraphs, wherein the battery or cell is a VRLA battery or cell.

[0555] 15. The lead-acid battery or cell of any of paragraphs 1-4, 6, 7-9, 13, and 14, wherein the battery or cell is an absorbent glass mat (AGM) battery, wherein the separator comprises, consists essentially of, or consists of absorbent glass fiber mat.

[0556] 16. A lead-acid battery or battery cell according to any one of the preceding paragraphs, wherein the battery is a bipolar lead-acid battery.

[0557] 17. The lead-acid battery of paragraph 16, wherein the bipolar lead-acid battery comprises:

[0558] One or more bipolar plates, each bipolar plate comprising

[0559] Conductive substrate,

[0560] A positive electrode comprising a positive active material (PAM), and

[0561] a negative electrode comprising a negative active material (NAM),

[0562] wherein the positive electrode is located on a first surface of the conductive substrate, and the negative electrode is located on a second surface of the conductive substrate opposite to the first surface;

[0563] a positive terminal comprising a positive electrode optionally comprising a positive active material (PAM);

[0564] a negative terminal comprising a negative electrode optionally comprising a negative active material (NAM); and

[0565] a separator disposed between each of the negative electrode and the positive electrode;

[0566] The positive electrode and the negative electrode each have a pore diameter distribution measured by mercury porosimetry, and the separators each have a pore diameter distribution measured by capillary flow porometry,

[0567] The battery comprises at least one battery cell, wherein the pore diameter distribution of the positive electrode and / or the negative electrode is as defined in any one of paragraphs 1-16.

[0568] 18. A lead-acid battery or battery cell according to any one of paragraphs 1-8, 10, 11 and 13-17, wherein the separator has a pore diameter distribution measured by capillary flow porometry, wherein the pore diameter distribution of the positive and / or negative electrode includes a ratio of pore volume greater than the mode pore diameter of the separator to the total pore volume of at least 80% or 85%.

[0569] 19. A lead-acid battery or battery cell according to any of the preceding paragraphs, wherein the separator has a pore diameter distribution measured by capillary flow porometry, wherein the pore diameter distribution of the positive and / or negative electrode includes a ratio of pore volume greater than the mode pore diameter of the separator to the total pore volume of at least 85%.

[0570] 20. A lead-acid battery or battery cell according to any of the preceding paragraphs, wherein the separator has a pore diameter distribution measured by capillary flow porometry, wherein the separator has a mode pore diameter of less than or equal to about 20 μm, 18 μm, 16 μm, 15 μm, 14 μm, 13 μm, 12 μm, 11 μm, 10 μm, 9 μm, 8 μm, 7 μm, 6 μm, 5 μm, 4 μm, 3 μm, 2 μm or 1 μm.

[0571] 21. The lead acid battery or battery cell of any of the preceding paragraphs, wherein the separator has a pore diameter distribution as measured by capillary flow porometry, wherein the separator has a pore diameter distribution of about 1 to 20 μm, 1 to 18 μm, 1 to 16 μm, 1 to 15 μm, 1 to 14 μm, 1 to 13 μm, 1 to 12 μm, 1 to 11 μm, 1 to 10 μm, 1 to 9 μm, 1 to 8 μm, 1 to 7 μm, 1 to 6 μm, 1 to 5 μm, 2 to 20 μm, 2 to 18 μm, 2 to 16 μm, 2 to 15 μm, 2 to 14 μm, 2 to 13 μm, 2 to 12 μm, 2 to 11 μm, 2 to 10 μm, 2 to 9 μm, 2 to 8 μm, 2 to 7 μm, 2 to 6 μm, 2 to 5 μm, 3 to 20 μm, 3 to 18 μm, 3 to 16 μm, 3 to 15 μm, 3 to 14 μm, 3 to 13 μm, 3 to 12 μm, to 16μm, 3 to 15μm, 3 to 14μm, 3 to 13μm, 3 to 12μm, 3 to 11μm, 3 to 10μm, 3 to 9μm, 3 to 8μm, 3 to 7μm, 3 to 6μm, 3 to 5μm, 4 to 20μm, 4 to 18μm, 4 to 16μm, 4 to 15μm, 4 to 14μm, 4 to 13μm, 4 to 12μm, 4 to 11μm The majority pore diameters are 4 to 10 μm, 4 to 9 μm, 4 to 8 μm, 4 to 7 μm, 4 to 6 μm, 4 to 5 μm, 5 to 20 μm, 5 to 18 μm, 5 to 16 μm, 5 to 15 μm, 5 to 14 μm, 5 to 13 μm, 5 to 12 μm, 5 to 11 μm, 5 to 10 μm, 5 to 9 μm, 5 to 8 μm, 5 to 7 μm or 5 to 6 μm.

[0572] 22. A lead-acid battery or cell according to any of the preceding paragraphs, wherein the positive electrode and / or negative electrode is formed from a slurry having a viscosity of about 1.5 g / cm 3 Up to 5g / cm 3 or about 1.5g / cm 3 Up to 5.5g / cm 3 density.

[0573] 23. A lead-acid battery or cell according to any of the preceding paragraphs, wherein at least the negative electrode comprises the pore diameter distribution.

[0574] 24. An electrode for a lead acid battery or cell comprising an active material and having a pore diameter distribution as measured by mercury porosimetry, wherein the pore diameter distribution comprises a ratio of the volume of pores having a pore diameter greater than 20 μm to at least 15% of the total pore volume.

[0575] 25. An electrode for a lead-acid battery or battery cell comprising an active material and having a pore diameter distribution measured by mercury porosimetry, wherein the pore diameter distribution of the positive electrode and / or the negative electrode comprises at least 0.020 ml / g of volume of pores having a pore diameter greater than 20 μm.

[0576] 26. An electrode for a lead-acid battery or cell comprising an active material and having a pore diameter distribution as measured by mercury porosimetry, wherein the pore diameter distribution comprises:

[0577] (a) the ratio of the volume of pores having a pore diameter greater than 10 μm to the total pore volume is at least 50%, 55%, 60%, 65% or 70%;

[0578] (b) the ratio of the volume of pores having a pore diameter greater than 15 μm to the total pore volume is at least 25%, 30%, 35%, 40%, 45%, 50% or 55%;

[0579] (c) the ratio of the volume of pores having a pore diameter greater than 20 μm to the total pore volume is at least 15%, 20%, 25%, 30%, 40% or 45%;

[0580] (d) the ratio of the volume of pores with a pore diameter greater than 25 μm to the total pore volume is at least 15%, 20%, 25% or 30%;

[0581] (e) the ratio of the volume of pores having a pore diameter greater than 30 μm to the total pore volume is at least 10%, 15%, 20% or 25%;

[0582] (f) the ratio of the volume of pores having a pore diameter greater than 35 μm to the total pore volume is at least 10%, 15% or 20%; or

[0583] (g) Any combination of two or more of (a) to (f).

[0584] 27. An electrode for a lead-acid battery or cell comprising an active material and having a pore diameter distribution as measured by mercury porosimetry, wherein the pore diameter distribution comprises:

[0585] (a) the volume of pores with a pore diameter greater than 10 μm is at least 0.070, 0.075, 0.080, 0.085, 0.090, 0.095, 0.100, 0.110 or 0.120 ml / g;

[0586] (b) the volume of pores with a pore diameter greater than 15 μm is at least 0.035, 0.040, 0.050, 0.060, 0.070, 0.080, 0.090 or 0.095 ml / g;

[0587] (c) a volume of pores with a pore diameter greater than 20 μm of at least 0.020, 0.025, 0.030, 0.035, 0.040, 0.045, 0.050, 0.055, 0.060, 0.065, 0.070, 0.075, 0.080, 0.085, 0.090, 0.095, or 0.100 ml / g;

[0588] (d) the volume of pores with a pore diameter greater than 25 μm is at least 0.015, 0.020, 0.025, 0.030, 0.035, 0.040 or 0.050 ml / g;

[0589] (e) the volume of pores with a pore diameter greater than 30 μm is at least 0.015, 0.020, 0.025, 0.030, 0.035, 0.040 ml / g;

[0590] (f) the volume of pores with a pore diameter greater than 35 μm is at least 0.010, 0.015, 0.020, 0.025 or 0.030 ml / g; or

[0591] (g) Any combination of two or more of (a) to (f).

[0592] 28. An electrode for a lead acid battery or cell comprising an active material and having a pore diameter distribution as measured by mercury porosimetry, wherein the pore diameter distribution comprises a ratio of the volume of pores having a pore diameter greater than 10 μm to at least 50% of the total pore volume.

[0593] 29. An electrode for a lead-acid battery or cell comprising an active material and having a pore diameter distribution as measured by mercury porosimetry, wherein the pore diameter distribution comprises:

[0594] (a) the ratio of the volume of pores having a pore diameter greater than 2 μm to the total pore volume is at least 85%;

[0595] (b) the ratio of the volume of pores having a pore diameter greater than 3 μm to the total pore volume is at least 80%;

[0596] (c) the ratio of the volume of pores having a pore diameter greater than 4 μm to the total pore volume is at least 75%;

[0597] (d) the ratio of the volume of pores having a pore diameter greater than 5 μm to the total pore volume is at least 75%;

[0598] (e) the ratio of the volume of pores having a pore diameter greater than 6 μm to the total pore volume is at least 70%;

[0599] (f) the ratio of the volume of pores having a pore diameter greater than 7 μm to the total pore volume is at least 70%;

[0600] (g) the ratio of the volume of pores with a pore diameter greater than 8 μm to the total pore volume is at least 65%;

[0601] (h) the ratio of the volume of pores having a pore diameter greater than 9 μm to the total pore volume is at least 55%;

[0602] (i) the ratio of the volume of pores having a pore diameter greater than 10 μm to the total pore volume is at least 50%; or

[0603] (j) Any combination of two or more of (a) to (i).

[0604] 30. An electrode according to any one of paragraphs 24 to 29, wherein the electrode is a negative electrode.

[0605] 31. A lead-acid battery or cell or electrode according to any of the preceding paragraphs, wherein the pore diameter distribution comprises:

[0606] (a) the ratio of the volume of pores having a pore diameter greater than 10 μm to the total pore volume is at least 50%, 55%, 60%, 65% or 70%;

[0607] (b) the ratio of the volume of pores having a pore diameter greater than 20 μm to the total pore volume is at least 15%, 20%, 25%, 30%, 40% or 45%; and

[0608] (c) the ratio of the volume of pores having a pore diameter greater than 30 μm to the total pore volume is at least 10%, 15%, 20% or 25%;

[0609] 32. A lead-acid battery or cell or electrode according to any of the preceding paragraphs, wherein the pore diameter distribution comprises:

[0610] (a) the ratio of the volume of pores having a pore diameter greater than 20 μm to the total pore volume is at least 15%, 20%, 25%, 30%, 40% or 45%; and

[0611] (b) the ratio of the volume of pores having a pore diameter greater than 30 μm to the total pore volume is at least 10%, 15%, 20% or 25%;

[0612] 33. A lead acid battery or cell or electrode according to any of the preceding paragraphs, wherein the pore diameter distribution comprises:

[0613] (a) the ratio of the volume of pores having a pore diameter greater than 20 μm to the total pore volume is at least 15%, 20%, 25%, 30%, 40% or 45%;

[0614] (b) the ratio of the volume of pores having a pore diameter greater than 25 μm to the total pore volume is at least 15%, 20%, 25% or 30%; and

[0615] (c) the ratio of the volume of pores having a pore diameter greater than 30 μm to the total pore volume is at least 10%, 15%, 20% or 25%;

[0616] 34. A lead-acid battery or cell or electrode according to any of the preceding paragraphs, wherein the pore diameter distribution comprises:

[0617] (a) the volume of pores with a pore diameter greater than 10 μm is at least 0.070, 0.075, 0.080, 0.085, 0.090, 0.095, 0.100, 0.110 or 0.120 ml / g;

[0618] (b) the volume of pores with pore diameters greater than 20 μm is at least 0.020, 0.025, 0.030, 0.035, 0.040, 0.045, 0.050, 0.055, 0.060, 0.065, 0.070, 0.075, 0.080, 0.085, 0.090, 0.095, or 0.100 ml / g; and

[0619] (c) the volume of pores with a pore diameter greater than 30 μm is at least 0.015, 0.020, 0.025, 0.030, 0.035, 0.040 ml / g.

[0620] 35. A lead acid battery or cell or electrode according to any of the preceding paragraphs, wherein the pore diameter distribution comprises:

[0621] (a) the volume of pores with a pore diameter greater than 20 μm is at least 0.020, 0.025, 0.030, 0.035, 0.040, 0.045, 0.050, 0.055, 0.060, 0.065, 0.070, 0.075, 0.080, 0.085, 0.090, 0.095 or 0.100 ml / g; and

[0622] (b) the volume of pores with a pore diameter greater than 30 μm is at least 0.015, 0.020, 0.025, 0.030, 0.035, 0.040 ml / g.

[0623] 36. A lead acid battery or cell or electrode according to any of the preceding paragraphs, wherein the pore diameter distribution comprises:

[0624] (a) the volume of pores with a pore diameter greater than 20 μm is at least 0.020, 0.025, 0.030, 0.035, 0.040, 0.045, 0.050, 0.055, 0.060, 0.065, 0.070, 0.075, 0.080, 0.085, 0.090, 0.095 or 0.100 ml / g;

[0625] (b) the volume of pores with a pore diameter greater than 25 μm is at least 0.015, 0.020, 0.025, 0.030, 0.035, 0.040 or 0.050 ml / g; and

[0626] (c) the volume of pores with a pore diameter greater than 30 μm is at least 0.015, 0.020, 0.025, 0.030, 0.035, 0.040 ml / g.

[0627] 37. A lead-acid battery or battery cell or electrode according to any one of paragraphs 2-36, wherein the pore diameter distribution of the electrode or the positive and / or negative electrode includes a ratio of the volume of pores with a pore diameter greater than 20 μm to the total pore volume of at least 15%, 20%, 25%, 30%, 40% or 45%.

[0628] 38. A lead-acid battery or battery cell or electrode according to any of the preceding paragraphs, wherein the pore diameter distribution of the electrode or the positive and / or negative electrode comprises a ratio of the volume of pores with a pore diameter greater than 20 μm to the total pore volume of at least 20%, 25%, 30%, 40% or 45%.

[0629] 39. A lead-acid battery or battery cell or electrode according to any of the preceding paragraphs, wherein the pore diameter distribution of the electrode or the positive and / or negative electrode comprises a ratio of the volume of pores having a pore diameter greater than 20 μm to the total pore volume of at least 30%, 40% or 45%.

[0630] 40. A lead-acid battery or battery cell or electrode according to any one of paragraphs 1 and 3-39, wherein the pore diameter distribution of the electrode or the positive and / or negative electrode includes at least 0.020, 0.025, 0.030, 0.035, 0.040, 0.045, 0.050, 0.055, 0.060, 0.065, 0.070, 0.075, 0.080, 0.085, 0.090, 0.095 or 0.100 ml / g of the volume of pores with a pore diameter greater than 20 μm.

[0631] 41. A lead-acid battery or battery cell or electrode according to any of the preceding paragraphs, wherein the pore diameter distribution of the electrode or the positive and / or negative electrode includes at least 0.030, 0.035, 0.040, 0.045, 0.050, 0.055, 0.060, 0.065, 0.070, 0.075, 0.080, 0.085, 0.090, 0.095 or 0.100 ml / g of the volume of pores with a pore diameter greater than 20 μm.

[0632] 42. A lead-acid battery or battery cell or electrode according to any of the preceding paragraphs, wherein the pore diameter distribution of the electrode or the positive and / or negative electrode includes at least 0.040, 0.045, 0.050, 0.055, 0.060, 0.065, 0.070, 0.075, 0.080, 0.085, 0.090, 0.095 or 0.100 ml / g of the volume of pores with a pore diameter greater than 20 μm.

[0633] 43. A lead-acid battery or battery cell or electrode according to any of the preceding paragraphs, wherein the pore diameter distribution of the electrode or the positive and / or negative electrode comprises a total pore volume of at least about 0.135, 0.140, 0.145, 0.150, 0.155, 0.160, 0.165, 0.170, 0.175, 0.180, 0.185, 0.190, 0.195 or 0.200 ml / g.

[0634] 44. A lead-acid battery or battery cell or electrode according to any of the preceding paragraphs, wherein the pore diameter distribution of the electrode or the positive and / or negative electrode comprises a total pore volume of at least about 0.150, 0.155, 0.160, 0.165, 0.170, 0.175, 0.180, 0.185, 0.190, 0.195 or 0.200 ml / g.

[0635] 45. A lead-acid battery or battery cell or electrode according to any of the preceding paragraphs, wherein the electrode or positive and / or negative electrode having the pore diameter distribution is formed from a slurry having a lead oxide content of not more than 85% or not more than 84%.

[0636] 46. ​​A lead-acid battery or battery cell or electrode according to any one of paragraphs 1-6, 8, 9, 11-45, wherein the pore diameter distribution of the electrode or the positive and / or negative electrode includes a ratio of the volume of pores with a pore diameter greater than 10 μm to the total pore volume of at least 50%, 55%, 60%, 65% or 70%.

[0637] 47. A lead-acid battery or battery cell or electrode according to any of the preceding paragraphs, wherein the pore diameter distribution of the electrode or the positive and / or negative electrode comprises at least 0.070, 0.075, 0.080, 0.085, 0.090, 0.095, 0.100, 0.110 or 0.120 ml / g of the volume of pores having a pore diameter greater than 10 μm.

[0638] 48. A lead-acid battery or battery cell or electrode according to any of the preceding paragraphs, wherein the pore diameter distribution of the electrode or the positive and / or negative electrode comprises at least 0.070, 0.075, 0.080, 0.085, 0.090, 0.095, 0.100, 0.110 or 0.120 ml / g of the volume of pores having a pore diameter greater than 10 μm.

[0639] 49. A lead-acid battery or battery cell or electrode according to any of the preceding paragraphs, wherein the electrode or the electrode or the positive and / or negative electrode has a pore diameter distribution comprising a ratio of the volume of pores having a pore diameter greater than 15 μm to the total pore volume of at least 25%, 30%, 35%, 40%, 45%, 50% or 55%.

[0640] 50. A lead-acid battery or battery cell or electrode according to any of the preceding paragraphs, wherein the electrode or the electrode or the positive and / or negative electrode has a pore diameter distribution comprising a ratio of the volume of pores having a pore diameter greater than 15 μm to the total pore volume of at least 45%, 50% or 55%.

[0641] 51. A lead-acid battery or battery cell or electrode according to any of the preceding paragraphs, wherein the pore diameter distribution of the electrode or the positive and / or negative electrode includes at least 0.035, 0.040, 0.050, 0.060, 0.070, 0.080, 0.090 or 0.095 ml / g of the volume of pores with a pore diameter greater than 15 μm.

[0642] 52. A lead-acid battery or battery cell or electrode according to any of the preceding paragraphs, wherein the pore diameter distribution of the electrode or the positive and / or negative electrode comprises at least 0.070, 0.080, 0.090 or 0.095 ml / g of the volume of pores having a pore diameter greater than 15 μm.

[0643] 53. A lead-acid battery or battery cell or electrode according to any of the preceding paragraphs, wherein the electrode or the electrode or the positive and / or negative electrode has a pore diameter distribution comprising a ratio of the volume of pores having a pore diameter greater than 25 μm to the total pore volume of at least 15%, 20%, 25% or 30%.

[0644] 54. A lead-acid battery or battery cell or electrode according to any of the preceding paragraphs, wherein the electrode or the electrode or the positive and / or negative electrode has a pore diameter distribution comprising a ratio of the volume of pores having a pore diameter greater than 25 μm to the total pore volume of at least 20%, 25% or 30%.

[0645] 55. A lead-acid battery or battery cell or electrode according to any of the preceding paragraphs, wherein the pore diameter distribution of the electrode or the positive and / or negative electrode includes at least 0.015, 0.020, 0.025, 0.030, 0.035, 0.040 or 0.050 ml / g of the volume of pores with a pore diameter greater than 25 μm.

[0646] 56. A lead-acid battery or battery cell or electrode according to any of the preceding paragraphs, wherein the pore diameter distribution of the electrode or the positive and / or negative electrode comprises at least 0.025, 0.030, 0.035, 0.040 or 0.050 ml / g of the volume of pores having a pore diameter greater than 25 μm.

[0647] 57. A lead-acid battery or battery cell or electrode according to any of the preceding paragraphs, wherein the electrode or the electrode or the positive and / or negative electrode has a pore diameter distribution comprising a ratio of the volume of pores having a pore diameter greater than 30 μm to the total pore volume of at least 10%, 15%, 20% or 25%.

[0648] 58. A lead-acid battery or battery cell or electrode according to any of the preceding paragraphs, wherein the electrode or the electrode or the positive and / or negative electrode has a pore diameter distribution comprising a ratio of the volume of pores having a pore diameter greater than 30 μm to the total pore volume of at least 15%, 20% or 25%.

[0649] 59. A lead-acid battery or battery cell or electrode according to any of the preceding paragraphs, wherein the pore diameter distribution of the electrode or the positive and / or negative electrode comprises at least 0.015, 0.020, 0.025, 0.030, 0.035, 0.040 ml / g of the volume of pores with a pore diameter greater than 30 μm.

[0650] 60. A lead-acid battery or battery cell or electrode according to any of the preceding paragraphs, wherein the pore diameter distribution of the electrode or the positive and / or negative electrode comprises at least 0.020, 0.025, 0.030, 0.035, 0.040 ml / g of the volume of pores with a pore diameter greater than 30 μm.

[0651] 61. A lead-acid battery or battery cell or electrode according to any of the preceding paragraphs, wherein the electrode or the electrode or the positive and / or negative electrode has a pore diameter distribution comprising a ratio of the volume of pores having a pore diameter greater than 35 μm to the total pore volume of at least 10%, 15% or 20%.

[0652] 62. A lead-acid battery or battery cell or electrode according to any of the preceding paragraphs, wherein the pore diameter distribution of the electrode or the positive and / or negative electrode comprises at least 0.010, 0.015, 0.020, 0.025 or 0.030 ml / g of the volume of pores having a pore diameter greater than 35 μm.

[0653] 63. A lead-acid battery or battery cell or electrode according to any of the preceding paragraphs, wherein the pore diameter distribution of the electrode or the positive and / or negative electrode comprises at least 0.015, 0.020, 0.025 or 0.030 ml / g of the volume of pores having a pore diameter greater than 35 μm.

[0654] 64. A lead-acid battery or battery cell or electrode according to any of the preceding paragraphs, wherein the electrode or the positive and / or negative electrode has a pore diameter distribution comprising at least 50%, 55%, 60%, 65% or 70% of the volume of pores having a pore diameter greater than 10 μm to the total pore volume; and

[0655] (a) the ratio of the volume of pores having a pore diameter greater than 2 μm to the total pore volume is at least 85% or 90%;

[0656] (b) the ratio of the volume of pores having a pore diameter greater than 3 μm to the total pore volume is at least 80% or 85%;

[0657] (c) the ratio of the volume of pores having a pore diameter greater than 4 μm to the total pore volume is at least 75%, 80% or 85%;

[0658] (d) the ratio of the volume of pores having a pore diameter greater than 5 μm to the total pore volume is at least 75%, 80% or 85%;

[0659] (e) the ratio of the volume of pores having a pore diameter greater than 6 μm to the total pore volume is at least 70%, 75% or 80%;

[0660] (f) the ratio of the volume of pores having a pore diameter greater than 7 μm to the total pore volume is at least 70%, 75% or 80%;

[0661] (g) the ratio of the volume of pores having a pore diameter greater than 8 μm to the total pore volume is at least 65%, 70% or 75%;

[0662] (h) the ratio of the volume of pores having a pore diameter greater than 9 μm to the total pore volume is at least 55%, 60%, 65%, 70% or 75%; or

[0663] (i) Any combination of two or more of (a) to (h).

[0664] 65. A lead-acid battery or battery cell or electrode according to any of the preceding paragraphs, wherein the pore diameter distribution of the electrode or the positive and / or negative electrode comprises a ratio of the volume of pores greater than 10 μm to the total pore volume of at least 55%, 60%, 65% or 70%.

[0665] 66. A lead-acid battery or battery cell or electrode according to any of the preceding paragraphs, wherein the electrode or the electrode or the positive and / or negative electrode has a pore diameter distribution comprising a ratio of the volume of pores greater than 10 μm to the total pore volume of at least 65% or 70%.

[0666] 67. A lead-acid battery or battery cell or electrode according to any of the preceding paragraphs, wherein the electrode or the positive and / or negative electrode has a pore diameter distribution comprising a ratio of the volume of pores having a pore diameter greater than 1 μm to the total pore volume of at least 95%.

[0667] 68. A lead-acid battery or battery cell or electrode according to any of the preceding paragraphs, wherein the electrode or the positive and / or negative electrode has a pore diameter distribution comprising at least 85% or 90% of the volume of pores having a pore diameter greater than 2 μm to the total pore volume.

[0668] 69. A lead-acid battery or battery cell or electrode according to any of the preceding paragraphs, wherein the electrode or the positive and / or negative electrode has a pore diameter distribution comprising at least 80% or 85% of the volume of pores having a pore diameter greater than 3 μm to the total pore volume.

[0669] 70. A lead-acid battery or battery cell or electrode according to any of the preceding paragraphs, wherein the pore diameter distribution of the electrode or the positive and / or negative electrode comprises a ratio of the volume of pores having a pore diameter greater than 4 μm to the total pore volume of at least 75%, 80% or 85%.

[0670] 71. A lead-acid battery or battery cell or electrode according to any of the preceding paragraphs, wherein the pore diameter distribution of the electrode or the positive and / or negative electrode comprises a ratio of the volume of pores having a pore diameter greater than 5 μm to the total pore volume of at least 75%, 80% or 85%.

[0671] 72. A lead-acid battery or battery cell or electrode according to any of the preceding paragraphs, wherein the pore diameter distribution of the electrode or the positive and / or negative electrode comprises a ratio of the volume of pores having a pore diameter greater than 6 μm to the total pore volume of at least 70%, 75% or 80%.

[0672] 73. A lead-acid battery or battery cell or electrode according to any of the preceding paragraphs, wherein the pore diameter distribution of the electrode or the positive and / or negative electrode comprises a ratio of the volume of pores having a pore diameter greater than 7 μm to the total pore volume of at least 70%, 75% or 80%.

[0673] 74. A lead-acid battery or battery cell or electrode according to any of the preceding paragraphs, wherein the pore diameter distribution of the electrode or the positive and / or negative electrode comprises a ratio of the volume of pores having a pore diameter greater than 8 μm to the total pore volume of at least 65%, 70% or 75%.

[0674] 75. A lead-acid battery or battery cell or electrode according to any of the preceding paragraphs, wherein the pore diameter distribution of the electrode or the positive and / or negative electrode comprises a ratio of the volume of pores having a pore diameter greater than 9 μm to the total pore volume of at least 55%, 60%, 65%, 70% or 75%.

[0675] 76. A lead-acid battery or battery cell or electrode according to any of the preceding paragraphs, wherein the electrode or the positive and / or negative electrode has a pore diameter distribution comprising:

[0676] (a) the ratio of the volume of pores having a pore diameter greater than 3 μm to the total pore volume is at least 80%;

[0677] (b) the ratio of the volume of pores having a pore diameter greater than 5 μm to the total pore volume is at least 75%;

[0678] (c) the ratio of the volume of pores having a pore diameter greater than 7 μm to the total pore volume is at least 70%; and

[0679] (d) the ratio of the volume of pores having a pore diameter greater than 10 μm to the total pore volume is at least 50%;

[0680] 77. A lead-acid battery or battery cell or electrode according to any one of paragraphs 1-75, wherein the pore diameter distribution of the electrode or the positive electrode and / or negative electrode comprises:

[0681] (a) the ratio of the volume of pores having a pore diameter greater than 5 μm to the total pore volume is at least 75%; and

[0682] (b) The ratio of the volume of pores having a pore diameter greater than 10 μm to the total pore volume is at least 50%.

[0683] 78. A lead-acid battery or battery cell or electrode according to any one of paragraphs 1-75, wherein the pore diameter distribution of the electrode or the positive electrode and / or negative electrode comprises:

[0684] (a) the ratio of the volume of pores having a pore diameter greater than 5 μm to the total pore volume is at least 75%; and

[0685] (b) The ratio of the volume of pores having a pore diameter greater than 10 μm to the total pore volume is at least 55%.

[0686] 79. A lead-acid battery or battery cell or electrode according to any one of paragraphs 1-75, wherein the pore diameter distribution of the electrode or the positive electrode and / or negative electrode comprises:

[0687] (a) the ratio of the volume of pores having a pore diameter greater than 3 μm to the total pore volume is at least 80%;

[0688] (b) the ratio of the volume of pores having a pore diameter greater than 5 μm to the total pore volume is at least 75%;

[0689] (c) the ratio of the volume of pores having a pore diameter greater than 7 μm to the total pore volume is at least 70%; and

[0690] (d) the ratio of the volume of pores having a pore diameter greater than 10 μm to the total pore volume is at least 50%;

[0691] 80. A lead-acid battery or battery cell or electrode according to any one of paragraphs 1-75, wherein the pore diameter distribution of the electrode or the positive electrode and / or negative electrode comprises:

[0692] (a) the ratio of the volume of pores having a pore diameter greater than 3 μm to the total pore volume is at least 80%;

[0693] (b) the ratio of the volume of pores having a pore diameter greater than 5 μm to the total pore volume is at least 75%;

[0694] (c) the ratio of the volume of pores having a pore diameter greater than 10 μm to the total pore volume is at least 50%;

[0695] 81. An electrode according to any of the preceding paragraphs, wherein the electrode is composed of a density of about 1.5 to 5 g / cm 3 of slurry is formed.

[0696] 82. A bipolar plate for a bipolar lead-acid battery, comprising:

[0697] Conductive substrate,

[0698] A positive electrode comprising a positive active material (PAM), and

[0699] a negative electrode comprising a negative active material (NAM),

[0700] wherein the positive electrode is located on a first surface of the conductive substrate, and the negative electrode is located on a second surface of the conductive substrate opposite to the first surface; and

[0701] The positive electrode and / or the negative electrode is an electrode as described in any one of the preceding paragraphs.

[0702] 83. A battery or battery cell, electrode or plate according to any of the preceding paragraphs, wherein the positive electrode and / or negative electrode comprises an electrode frame in which the active material is disposed.

[0703] 84. A battery or battery cell, electrode or plate according to paragraph 83, wherein the electrode frame comprises a fibrous material.

[0704] 85. The battery or battery cell, electrode or plate according to paragraph 84, wherein the fiber material has a thickness of about 0.05 g / cm 3 Up to 0.2g / cm 3 , 0.07g / cm 3 Up to 0.17g / cm 3 , or 0.08g / cm 3 Up to 0.15g / cm 3 The bulk density.

[0705] 86. A method of manufacturing a lead acid battery or battery cell according to any one of the preceding paragraphs, the method comprising:

[0706] Providing a positive electrode including a positive electrode active material oxide (PAM oxide) slurry, a negative electrode including a negative electrode active material oxide (NAM oxide) slurry, and a separator capable of fixing an electrolyte;

[0707] Assembling a battery or battery cell from a positive electrode, a negative electrode and a separator;

[0708] adding electrolytes; and

[0709] The battery or cell is subjected to an initial cell or battery charge to form a cell.

[0710] 87. A method according to paragraph 86, wherein providing at least one positive electrode and / or at least one negative electrode includes applying a positive active material oxide (PAM oxide) slurry or a negative active material oxide (NAM oxide) slurry to an electrode frame.

[0711] 88. A method of making an electrode according to any of the preceding paragraphs, the method comprising applying a positive active material oxide (PAM oxide) slurry or a negative active material oxide (NAM oxide) slurry to an electrode frame.

[0712] 89. A method according to paragraph 87 or paragraph 88, wherein the slurry is applied to the electrode frame in a defined slurrying area.

[0713] 90. The method according to any one of paragraphs 86 to 89, wherein the slurry has a viscosity of about 1.5 to 5 g / cm 3 density.

[0714] Having described the invention above, including its preferred forms, changes and modifications apparent to those skilled in the art are intended to be included within the scope of the invention as defined by the appended claims.

[0715] Any documents mentioned herein, including but not limited to patents, patent applications, journal articles, books, etc., are incorporated herein by reference in their entirety. Any section headings used herein are for organizational purposes only and are not to be construed as limiting the subject matter described.

Claims

1. A lead-acid battery or cell, wherein the battery or cell is a non-gel lead-acid battery or cell or an absorbent glass mat (AGM) lead-acid battery or cell, comprising: a positive electrode comprising a positive active material (PAM); a negative electrode comprising a negative active material (NAM); as well as a separator capable of fixing an electrolyte disposed between the positive electrode and the negative electrode, The positive electrode and the negative electrode each have a pore diameter distribution measured by mercury porosimetry, The pore diameter distribution of the positive electrode and / or the negative electrode comprises a ratio of the volume of pores having a pore diameter greater than 20 μm to the total pore volume of at least 15%.

2. A lead-acid battery or cell, wherein the battery or cell is a non-gel lead-acid battery or cell or an absorbent glass mat (AGM) lead-acid battery or cell, comprising: a positive electrode comprising a positive active material (PAM); a negative electrode comprising a negative active material (NAM); as well as a separator capable of fixing an electrolyte disposed between the positive electrode and the negative electrode, The positive electrode and the negative electrode each have a pore diameter distribution measured by mercury porosimetry, The pore diameter distribution of the positive electrode and / or the negative electrode includes at least 0.020 ml / g of the volume of pores having a pore diameter greater than 20 μm.

3. The lead-acid battery or battery cell of claim 1 or 2, wherein the negative electrode has the pore diameter distribution, or both the negative electrode and the positive electrode have the pore diameter distribution.

4. A lead-acid battery or cell according to any one of the preceding claims, wherein the battery or cell is an absorbent glass mat (AGM) battery, wherein the separator comprises, consists essentially of, or consists of absorbent glass mat.

5. A lead acid battery or battery cell according to any one of the preceding claims, wherein the battery is a bipolar lead acid battery.

6. A lead-acid battery or battery cell according to any one of the preceding claims, wherein the separator has a pore diameter distribution measured by capillary flow porometry, wherein the pore diameter distribution of the positive and / or negative electrode comprises a ratio of the volume of pores greater than the mode pore diameter of the separator to the total pore volume of at least 80% or 85%.

7. The lead-acid battery or battery cell of any of the preceding claims, wherein the separator has a pore diameter distribution as measured by capillary flow porometry, wherein the separator has a mode pore diameter of less than or equal to about 20 μm, 18 μm, 16 μm, 15 μm, 14 μm, 13 μm, 12 μm, 11 μm, 10 μm, 9 μm, 8 μm, 7 μm, 6 μm, 5 μm, 4 μm, 3 μm, 2 μm, or 1 μm.

8. A lead acid battery or cell according to any one of the preceding claims, wherein the positive electrode and / or negative electrode is formed from a slurry having a viscosity of about 1.5 g / cm 3 Up to 5g / cm 3 or about 1.5g / cm 3 Up to 5.5g / cm 3 density.

9. An electrode for a lead acid battery or cell comprising an active material and having a pore diameter distribution as measured by mercury porosimetry, wherein the pore diameter distribution comprises a ratio of the volume of pores having a pore diameter greater than 20 μm to the total pore volume of at least 15%.

10. An electrode for a lead-acid battery or battery cell, comprising an active material and having a pore diameter distribution measured by mercury porosimetry, wherein the pore diameter distribution of the positive electrode and / or the negative electrode comprises a volume of pores having a pore diameter greater than 20 μm of at least 0.020 ml / g.

11. A lead-acid battery or battery cell or electrode according to any of the preceding claims, wherein the pore diameter distribution of the electrode or the pore diameter distribution of the positive and / or negative electrode comprises a ratio of the volume of pores with a pore diameter greater than 10 μm to the total pore volume of at least 50%, 55%, 60%, 65% or 70%.

12. A lead-acid battery or battery cell or electrode according to any one of the preceding claims, wherein the pore diameter distribution of the positive and / or negative electrode comprises at least 0.070, 0.075, 0.080, 0.085, 0.090, 0.095, 0.100, 0.110 or 0.120 ml / g of volume of pores having a pore diameter greater than 10 μm.

13. A lead-acid battery or battery cell or electrode according to any of the preceding claims, wherein the pore diameter distribution of the electrode or the pore diameter distribution of the positive and / or negative electrode comprises a ratio of the volume of pores with a pore diameter greater than 15 μm to the total pore volume of at least 25%, 30%, 35%, 40%, 45%, 50% or 55%.

14. A lead acid battery or battery cell or electrode according to any one of the preceding claims, wherein the pore diameter distribution of the positive and / or negative electrode comprises at least 0.035, 0.040, 0.050, 0.060, 0.070, 0.080, 0.090 or 0.095 ml / g of volume of pores having a pore diameter greater than 15 μm.

15. A lead-acid battery or battery cell or electrode according to any one of the preceding claims, wherein the pore diameter distribution of the electrode or the pore diameter distribution of the positive and / or negative electrode comprises a ratio of the volume of pores with a pore diameter greater than 25 μm to the total pore volume of at least 15%, 20%, 25% or 30%.

16. A lead acid battery or battery cell or electrode according to any one of the preceding claims, wherein the pore diameter distribution of the positive and / or negative electrode includes a volume of pores having a pore diameter greater than 25 μm of at least 0.015, 0.020, 0.025, 0.030, 0.035, 0.040 or 0.050 ml / g.

17. A lead-acid battery or battery cell or electrode according to any one of the preceding claims, wherein the pore diameter distribution of the electrode or the pore diameter distribution of the positive and / or negative electrode comprises a ratio of the volume of pores with a pore diameter greater than 30 μm to the total pore volume of at least 10%, 15%, 20% or 25%.

18. A lead acid battery or battery cell or electrode according to any one of the preceding claims, wherein the pore diameter distribution of the positive and / or negative electrode comprises at least 0.015, 0.020, 0.025, 0.030, 0.035, 0.040 ml / g of volume of pores having a pore diameter greater than 30 μm.

19. A lead-acid battery or battery cell or electrode according to any one of the preceding claims, wherein the pore diameter distribution of the electrode or the pore diameter distribution of the positive and / or negative electrode comprises a ratio of the volume of pores with a pore diameter greater than 35 μm to the total pore volume of at least 10%, 15% or 20%.

20. A lead acid battery or battery cell or electrode according to any one of the preceding claims, wherein the pore diameter distribution of the positive and / or negative electrode comprises a volume of pores having a pore diameter greater than 35 μm of at least 0.010, 0.015, 0.020, 0.025 or 0.030 ml / g.

21. A lead acid battery or battery cell or electrode according to any one of the preceding claims, wherein the pore diameter distribution of the electrode or the pore diameter distribution of the positive and / or negative electrode comprises: (a) the ratio of the volume of pores having a pore diameter greater than 5 μm to the total pore volume is at least 75%; as well as (b) The ratio of the volume of pores having a pore diameter greater than 10 μm to the total pore volume is at least 50%.

22. A bipolar plate for a bipolar lead-acid battery, comprising: Conductive substrate, A positive electrode comprising a positive active material (PAM), and a negative electrode comprising a negative active material (NAM), wherein the positive electrode is located on a first surface of the conductive substrate, and the negative electrode is located on a second surface of the conductive substrate opposite to the first surface; and The positive electrode and / or the negative electrode is an electrode according to any one of the preceding claims.

23. A battery or battery cell, electrode or plate according to any preceding claim, wherein the positive electrode and / or negative electrode comprises an electrode frame in which the active material is disposed.

24. The battery or battery cell, electrode or plate of claim 23, wherein the electrode frame comprises a fibrous material.

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