Patent Description:
The invention(s) described herein relate to the field of battery paste and electrolyte compositions. More specifically the invention(s) described herein relate to an AGM lead acid battery having said battery paste and electrolyte compositions.

Lead acid batteries are known and are often used for starting- iighting-ign its on (SLI) functions as well as deep cycle (DC) related applications. Conventionally, lead acid batteries include electrically conductive positive and negative current collectors in the form of lead or lead-alloy grids. These current collectors or grids have a paste composition deposited, thereon, with the makeup or composition of the paste potentially varying based upon the make-up of the current collector (e.g., a negative paste on a negative grid and a positive paste on a positive grid). Lead acid batteries also include an electrolyte which is normally acidic in nature and commonly is or includes aqueous solutions of H2SO4. Lead acid batteries may also include a separator between grids and/or an absorbent glass mat (AOM) wrapped around one or more said grids.

A need exists for an electrochemical cell which provides improved performance in a flat plate AGM lead acid battery.

The document <CIT> relates to a battery paste composition and a lead-acid electrochemical cell which incorporates the composition. The cell includes a positive current collector and a negative current collector which are each coated with a paste containing one or more lead-containing compositions and a paste vehicle to form a positive plate and a negative plate.

The document <CIT> discloses an unformed paste-type positive electrode plate and an unformed paste-type negative electrode plate, which are laminated via a separator.

The document <CIT> relates to a method of manufacturing a lead storage battery which exhibits a high utilization rate of an active material of a positive electrode plate.

The present invention relates to an electrochemical cell according to independent claim <NUM>, wherein further developments of the inventive electrochemical cell are provided in the corresponding sub-claims.

The present invention further relates to a lead acid battery according to claim <NUM>, wherein further developments of the inventive lead acid battery are provided in claims <NUM> and <NUM>.

Battery paste and electrolyte compositions are disclosed, as well as an electrochemical cell for use therewith, the combination of which provides improved performance in a flat plate AGM lead acid battery.

An electrochemical cell is disclosed. The electrochemical cell includes a flat positive plate composed of a grid formed of virgin lead or high purity lead or highly purified secondary lead and a positive battery paste disposed on the grid. The battery paste comprises a lead-containing composition, a positive plate paste vehicle, and a polyvinylsulfonate additive. A flat negative plate is also provided which is composed of a grid and a negative battery paste disposed on the grid. The battery paste comprises a lead-containing composition and a negative plate paste vehicle. An absorbent glass mat is interleaved between the flat positive plate and the flat negative plate and an electrolyte is provided in the container and retained in the absorbent glass mat. The electrolyte includes phosphoric acid.

A lead acid battery is also disclosed. The battery includes a container and a plurality of electrochemical cells within the container. The electrochemical cells have a plurality of flat positive plates each composed of a grid formed of virgin lead or high purity lead or highly purified secondary lead and a positive battery paste disposed on the grid, the battery paste comprising a lead-containing composition, a positive plate paste vehicle, and a polyvinylsulfonate additive. The electrochemical cells also have a plurality of flat negative plates each composed of a grid and a negative battery paste disposed on the grid, the battery paste comprising a lead-containing composition and a negative plate paste vehicle. An absorbent glass mat is interleaved between the flat positive plate and the flat negative plate. An electrolyte is provided in the container and retained in the absorbent glass mat. The electrolyte includes phosphoric acid. The plurality of flat positive plates and the plurality of flat negative plates are connected by intercell connectors and coupled to one or more terminals. A lid is provided on the container.

An additional lead acid battery is disclosed including a container and a plurality of electrochemical cells within the container. The electrochemical cells include a plurality of flat positive plates each composed of a grid formed of virgin lead or high purity lead or highly purified secondary lead and a positive battery paste disposed on the grid. The battery paste comprises a lead-containing composition, a positive plate paste vehicle, and a polyvinylsulfonate additive. The battery also includes a plurality of flat negative plates each composed of a grid and a negative battery paste disposed on the grid. The battery paste comprises a lead-containing composition, a negative plate paste vehicle, an expander, and a polyvinylsulfonate additive. An absorbent glass mat is interleaved between the flat positive plate and the flat negative plate. An electrolyte is provided in the container and retained in the absorbent glass mat. The electrolyte includes phosphoric acid, water, sulfuric acid, and sodium sulfate. The plurality of flat positive plates and the plurality of flat negative plates are connected by intercell connectors and coupled to one or more terminals. A lid is provided on the container.

These and other features and advantages of devices, systems, and methods according to this invention are described in, or are apparent from, the following detailed descriptions of various examples of embodiments.

Various examples of embodiments of the systems, devices, and methods according to this invention will be described in detail, with reference to the following figures, wherein:.

In certain instances, details that are not necessary to the understanding of the invention or render other details difficult to perceive may have been omitted. It should be understood, of course, that the invention is not necessarily limited to the particular embodiments illustrated herein.

An improved electrochemical cell having a battery paste composition and electrolyte composition is described. More specifically, a flat plate AGM lead acid electrochemical cell for a battery having an improved paste composition and an electrolyte composition is described.

The electrochemical reaction that takes place within the electrochemical cell may be, in part, the result of the reaction of the various chemical compositions therein, including for example, the grid material, the battery paste composition, and the electrolyte. Various chemical compositions are further detailed herein as used in a flat plate AGM lead acid electrochemical cell and battery.

Generally, a battery <NUM> or electrochemical cell <NUM> is provided and shown in <FIG>. The battery <NUM> is an AGM battery having positive and negative plates <NUM>, <NUM> which are separated by an absorbent glass mat <NUM> that absorbs and holds the battery's acid or electrolyte and prevents it from flowing freely inside the battery. Referring to <FIG>, the plates <NUM>, <NUM> include electrically-conductive positive or negative grids <NUM>, <NUM> or current collecting members. Positive paste <NUM> is provided on the positive grid <NUM> and negative paste <NUM> is provided on the negative grid <NUM>. More specifically, the positive plate <NUM> includes a positive grid <NUM> having or supporting a positive active material or paste <NUM> thereon, and in some examples of embodiments may include a pasting paper or a scrim <NUM>; and the negative plate <NUM> includes a negative grid <NUM> having or supporting a negative active material or paste <NUM> thereon, and in some examples of embodiments may include a pasting paper or a scrim <NUM>. Grid <NUM> or grids <NUM> and <NUM> are formed of pure or virgin lead or high purity lead or highly purified secondary lead. Positioned between the positive and negative plates <NUM>, <NUM> is a separator <NUM>. In a retained electrolyte-type battery system such as described herein, the separator <NUM> is a porous and absorbent glass mat (AGM). In some examples, the AGM <NUM> may also be used with an additional separator. As indicated, a pasting paper or pasting material or scrim <NUM> may also be used or provided on the plate to help retain the paste on the grid.

Individual battery cells or electrochemical cells <NUM> may be assembled by alternating one or more, and preferably a plurality of positive and negative plates <NUM>, <NUM> and separators <NUM> to form a plate block <NUM>. Each plate block <NUM> is positioned within a housing or container <NUM> of a battery <NUM> and connected by electrical connecting straps or intercell connectors <NUM> (e.g., cast on straps) to and between the cells <NUM>. The intercell connectors <NUM> are connected to lugs <NUM> which extend from the grids <NUM>, <NUM>. Electrolyte <NUM> is included in the housing <NUM> and more specifically is retained at least in part within the separator or AGM <NUM>. A lid <NUM> covers the housing or container <NUM>. In an AGM battery, the lid <NUM> may be sealed to the container <NUM>.

One or more positive and one or more negative terminals <NUM> may be provided. Such terminals typically include portions which may extend through the cover <NUM> and/or housing <NUM> and electrically couple to the intercell connectors <NUM> or electrochemical cells <NUM>, depending upon the battery design. It will be recognized that a variety of terminal arrangements are possible, including top, side or corner configurations known in the art.

According to the invention, the plate (both positive and negative) <NUM>, <NUM>, which includes the grid <NUM> or <NUM>, is a generally flat plate. The positive grid (or both positive and negative grids) <NUM>, <NUM> is composed of lead which is virgin lead (Pb) (i.e., from a mine rather than recycled lead), or high purity lead, or highly purified secondary lead, or may be substantially pure or virgin lead. In one example, the lead may also include a small amount of tin (Sn) added to the lead which may provide improved fluidity of the metal and some corrosion resistance. According to one or more examples of embodiments, the lead may be approximately <NUM>% lead. In one or more further examples of embodiments, tin in the range of approximately <NUM>% to approximately <NUM>% may be added to the lead.

A battery paste <NUM>, <NUM> composition is provided on or supported by the one or more battery grids or current collectors <NUM>, <NUM>. In one or more examples, the paste <NUM> or <NUM> may be provided in a layer of a predetermined amount on the battery grid <NUM> or <NUM>. An example of a suitable battery paste composition is disclosed in <CIT>. Generally, as described herein the battery paste composition comprises a positive paste <NUM> on the positive grid <NUM> or current collecting member (which forms the positive plate <NUM>) and a negative paste <NUM> on the negative grid <NUM> or current collecting member (which forms the negative plate <NUM>). To this end, the paste according to one or more examples of embodiments may be composed of virgin lead (Pb) (i.e., from a mine rather than recycled lead), or high purity lead, or highly purified secondary lead, or substantially pure or virgin lead. In one or more examples of embodiments, the lead may be approximately <NUM>% to <NUM>% lead. The paste composition(s) (e.g. the positive paste, the negative paste, or both pastes) may contain a specialized paste additive.

In more detail, the positive plate <NUM> contains a metal (e.g., lead) grid <NUM> with lead dioxide active material or paste <NUM> thereon. More specifically, the positive paste <NUM> disclosed herein generally includes at least one particulate lead-containing composition and a paste vehicle. Different materials may be used in connection with the lead-containing composition, with the present invention not being restricted to any particular materials or mixtures. The selected lead-containing composition or compositions may have a particle size of about <NUM>-<NUM> microns in a representative and non-limiting embodiment. One or more examples of lead-containing compositions which may be employed in the positive paste include, but are not limited to, finely-divided elemental Pb, PbO ("litharge" or "massicot"), Pb<NUM> O<NUM> ("red lead"), PbSO<NUM> ("lead sulfate" with the term "PbSO<NUM> " being defined to also include its associated hydrates), and mixtures thereof. These materials may be employed alone or in combination as determined by numerous factors, including for example, the intended use of the battery and the other materials employed in the battery. Accordingly, the term "lead-containing composition" is defined to encompass elemental lead, lead compounds, and mixtures thereof. The positive paste <NUM> also includes a paste vehicle which is primarily used as a carrier medium to produce the completed paste. In one or more examples of embodiments, water may be used as the paste vehicle. A representative positive paste <NUM> may include about <NUM>-<NUM>% by weight vehicle therein. In addition, the positive paste <NUM> may likewise contain an aqueous solution of H<NUM> SO<NUM> therein (e.g., about <NUM>-<NUM>) as an optional ingredient. However, variations on the materials included in the positive paste and/or any particular amounts/concentrations of this material may not depart from the overall scope of the present invention.

As previously indicated, a specialized paste additive is provided in at least the positive paste <NUM>, or in both the positive paste and the negative paste <NUM>. This additive involves a polymeric composition, such as "polyvinylsulfonic acid" or the salts of this material (e.g. "polyvinylsulfonates"). For example, polyvinylsulfonic acid may be chemically characterized in accordance with the following representative formula:.

In this formula, x=<NUM>-<NUM> and n=<NUM>-<NUM> in a preferred and non-limiting example of embodiments, with the term "polyvinylsulfonic acid" being defined to encompass all of the formulations included within these ranges. Likewise, the salts of polyvinylsulfonic acid (e.g. "polyvinylsulfonates") may be represented by the following formula:.

In the above-listed formula, M is an alkali metal or alkaline earth metal counterion preferably selected from the group consisting of Na+, K+, Li+, Ba+<NUM>, Mg+<NUM>, Ca+<NUM>, and Sr+<NUM>. Likewise, as noted above, x=<NUM>-<NUM> and n=<NUM>-<NUM> in a preferred and non-limiting example of embodiments, with the term "polyvinylsulfonate" being defined to encompass all of the formulations included within these ranges.

Polyvinylsulfonic acid and polyvinylsulfonates are available from a number of commercial sources (listed below), and are generally classified as "water-soluble ionomers" (e.g. polymers with ionic groups). Likewise, these materials are also broadly characterized as "polyelectrolytes" with an average molecular weight in a non-limiting, representative embodiment of about <NUM>-<NUM>,<NUM>. Polyvinylsulfonic acid and salts thereof (polyvinylsulfonates) are commercially available from many sources including but not limited to the Hoechst Company of Germany, Air Products Company of Allentown, Pa. (USA) and Nalco/Exxon of England (UK).

Polyvinylsulfonic acid and polyvinylsulfonates collectively provide numerous advantages when used in the paste compositions on the positive and/or negative current collecting members (e.g. grids) of an electrochemical cell. These benefits include, as non-limiting examples: the ability of these materials to function as "plasticizers" in which the sulfate groups therein effectively interlink particulate materials (e.g. the lead-containing compositions) in the pastes to produce a more cohesive paste product; an improvement in the overall charge capacity of the battery; an increase in battery cycle life; the production of more homogeneous, smooth, and uniform paste products which improves the overall efficiency of the paste application process; the control of extraneous crystal growth on the plates; and/or a general improvement in plate performance under normal and adverse (e.g. low temperature) operating conditions. Moreover, use of the claimed additive in the positive (and/or negative) paste generally improves the consistency of the paste. When added to the positive paste and/or negative paste, the additive may function as a "rheology modifier" which makes the paste smoother and more adhesive, thereby facilitating the paste application process.

The completed positive paste may have a typical density of about <NUM>-<NUM>/cc. One example of a positive paste <NUM> containing the desired additive composition is provided in Table I:.

The information in Table I is presented for purposes of example only and one of skill in the art will understand that variations thereon may be made without departing from the overall scope of the present invention.

The negative plate <NUM> may be composed of a metal (e.g., lead) grid <NUM> with a spongy lead active material or paste <NUM> thereon. The negative paste <NUM> may, in a preferred embodiment, be substantially similar to the positive paste with certain exceptions as outlined below. Like the positive paste, the lead of the negative paste <NUM> may be a pure or virgin lead, or substantially pure or virgin lead. In this regard, the lead may be approximately <NUM>% to <NUM>% lead. Exemplary lead-containing compositions which may be employed in the negative paste <NUM> include but are not limited to finely-divided elemental Pb, PbO ("litharge" or "massicot"), Pb<NUM> O<NUM> ("red lead"), PbSO<NUM> ("lead sulfate" with the term "PbSO<NUM>" being defined to also include its associated hydrates), and mixtures thereof. These materials may be employed alone or in combination as determined by numerous factors, including for example, the intended use of the battery and the other materials employed in the battery. Accordingly, the term "lead-containing composition" is defined to encompass elemental lead, lead compounds, and mixtures thereof.

If needed, the negative paste <NUM> may also include an optional "expander" which, for example, may be designed to promote paste uniformity and consistency, as well as long term or "cycling" performance. Representative materials suitable for this purpose include, but are not limited to, barium sulfate, carbon black, and lignosulfonate (which may consist of a non-water-soluble mononuclear phenylpropane derivative) and the like.

The completed negative paste <NUM> may have a typical density of about <NUM>-<NUM>/cc. One example of a negative paste <NUM> containing the desired additive composition is provided in Table II:.

The information in Table II is presented for purposes of example only and one of skill in the art will understand that variations thereon may be made without departing from the overall scope of the present invention.

It is also contemplated that the claimed additive may be absent from the negative paste and only present in the positive paste. To this end, the negative paste <NUM> without the additive may have the following example composition values: Particulate lead-containing composition: about <NUM>-<NUM>% by weight; H<NUM> SO<NUM>: about <NUM>-<NUM>% by weight; Expander: about <NUM>-<NUM>% by weight; and Paste vehicle (water): balance needed to make <NUM>%.

As indicated, an electrolyte <NUM> is also provided in the battery <NUM>. Generally, the electrolyte <NUM> may be a solution which is clear, colorless and free of particulate matter. The electrolyte <NUM> in one or more particular examples of embodiments may be composed of phosphoric acid which may be added to sulfuric acid and water. The electrolyte <NUM> according to one or more further examples of embodiments may be composed of phosphoric acid and/or sodium sulfate which are added to sulfuric acid and water. Preferably, the electrolyte <NUM> is composed of water, which may be deionized water, sulfuric acid, phosphoric acid, and sodium sulfate, and in some instances may include one or more impurities.

Phosphoric acid is present in the electrolyte <NUM> in a range of from <NUM>/L to <NUM>/L.

Various impurities, such as metal ions, may also be present. Examples of impurities may include, but are not limited to, Ag, As, Bi, Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pt, Sb, Se, Te, V, Zn, Chloride, TOC. Generally, in some examples the metal ions may not exceed a total concentration.

An electrolyte <NUM> as described above and used in association with a flat plate electrochemical cell <NUM> is unique to the present invention. More specifically, a unique flat plate AGM electrochemical cell <NUM> is described having a phosphoric acid in the electrolyte solution, and/or a phosphoric acid and sodium sulfate in the electrolyte solution. Such a combination has various advantages, including, for example improved performance of the electrochemical cell.

The electrochemical cell <NUM> includes an absorbent glass mat or AGM <NUM>. The mat or AGM <NUM> may be formed of any commercially known or future developed material and generally comprises a woven or non-woven mat of fibers composed of polymer and/or glass, such as but not limited to very fine fiberglass. Electrolyte <NUM> is, in part, absorbed by the mat <NUM> between the plates <NUM>, <NUM> and immobilized by the mat <NUM>, while keeping the electrolyte <NUM> available to the plates <NUM>, <NUM>, thereby allowing a fast reaction between the electrolyte <NUM> and plate material. To this end, the positive and negative plates <NUM>, <NUM> are separated by an absorbent glass mat <NUM> that absorbs and holds the electrolyte <NUM>. The saturation ratio of the electrolyte <NUM> in the mat <NUM> is improved over existing devices.

A battery <NUM> having one or more electrochemical cells <NUM> of the type described herein is shown in <FIG>. According to one or more examples of embodiments, the battery <NUM> is a lead acid storage battery. According to one or more further examples of embodiments, the lead acid storage battery <NUM> is a sealed lead acid battery or an AGM lead acid battery. While specific examples are described and illustrated, any secondary battery having the characteristics described herein may be acceptable for the purposes provided. The battery <NUM> in one or more examples of embodiments is configured to provide at least a portion of the power required to start or operate a vehicle and/or various vehicle systems. Further, it should be understood that the battery <NUM> may be utilized in a variety of applications not involving a vehicle, and all such applications are intended to be within the scope of the present disclosure.

As indicated, the battery <NUM> includes several electrochemical cells <NUM> which are provided in separate compartments of a container or housing <NUM>. The plurality of electrochemical cells <NUM> are electrically connected by intercell connectors <NUM> and terminals <NUM> are provided which are electrically connected to the cells <NUM> and which may extend through the lid <NUM> or container <NUM>. To this end, a cover or lid <NUM> is provided on the container <NUM>, and may be sealed thereto. In various embodiments, the lid <NUM> and/or container <NUM> includes terminal bushings, fill tubes, vent openings, and the like, as is customary for AGM batteries.

One or more examples of production of an electrochemical cell <NUM> having the foregoing components will now be described. As indicated, production of a battery <NUM> or electrochemical cell <NUM> includes obtaining electrically-conductive positive and negative grids <NUM>, <NUM> or current collecting members. Either or both the positive and negative grids <NUM>, <NUM> are, in one or more examples of embodiments, formed of virgin lead or high purity lead or highly purified secondary lead. Using conventional paste application techniques, the positive paste <NUM> is applied to the positive current collecting member <NUM> on both sides thereof (and within the openings in the grid or current collecting member). In a similar manner, the negative paste <NUM> is applied to the negative current collecting member <NUM> on both sides thereof (and within the openings in the grid or current collecting member).

Once the positive and negative current collecting members <NUM><NUM>, <NUM><NUM> are pasted in order to form the positive plate <NUM> and the negative plate <NUM>, individual cells <NUM> may be assembled. To this end, one or more, and preferably a plurality of positive and negative plates <NUM>, <NUM> are stacked together in an alternating manner, with a separator <NUM> positioned or interleaved between them or wrapped around one of said plates. In a retained electrolyte-type battery system such as disclosed herein, the separator <NUM> is a porous and absorbent mat (AGM) that is interleaved with the plates <NUM>, <NUM> or wrapped around at least a portion of one of the plates. A pasting paper or pasting material or scrim <NUM> may also be used, placed upon the plate <NUM> or <NUM> between the plate and the mat <NUM> to help retain the paste <NUM><NUM> or <NUM><NUM> on the grid <NUM><NUM> or <NUM><NUM>. Plate blocks <NUM> are formed by assembling a grouping of a plurality of positive and negative plates <NUM>, <NUM> in the manner described.

The plate blocks <NUM><NUM> are then positioned within the housing or container <NUM>, followed by connection of the electrical connecting straps or intercell connectors <NUM> (e.g., cast on straps) to and between the cells <NUM> and in particular to the respective lugs <NUM> on the grids; and electrolyte <NUM> addition (which may be retained within the separator member). The electrolyte solution is provided in the housing or container <NUM> between the electrode plates <NUM>, <NUM> (e.g., absorbed within the separator mat <NUM>). The lid <NUM> is then secured to the housing or container <NUM> followed by "formation" of the battery.

While a specific order of events is described for purposes of example, the invention is not limited thereto and variations in the order of events may be acceptable for the purposes provided.

As set forth above, an AGM battery having the foregoing chemical compositions provided in association with a flat plate electrochemical cell provides improved performance over existing devices.

As utilized herein, the terms "approximately," "about," "substantially", and similar terms are intended to have a broad meaning in harmony with the common and accepted usage by those of ordinary skill in the art to which the subject matter of this disclosure pertains.

It should be noted that references to relative positions (e.g., "top" and "bottom") in this description are merely used to identify various elements as are oriented in the Figures. It should be recognized that the orientation of particular components may vary greatly depending on the application in which they are used.

For the purpose of this disclosure, the term "coupled" means the joining of two members directly or indirectly to one another. Such joining may be stationary in nature or moveable in nature. Such joining may be achieved with the two members or the two members and any additional intermediate members being integrally formed as a single unitary body with one another or with the two members or the two members and any additional intermediate members being attached to one another. Such joining may be permanent in nature or may be removable or releasable in nature.

It is also important to note that the construction and arrangement of the system, methods, and devices as shown in the various examples of embodiments is illustrative only. Although only a few embodiments have been described in detail in this disclosure, those skilled in the art who review this disclosure will readily appreciate that many modifications are possible (e.g., variations in sizes, dimensions, structures, shapes and proportions of the various elements, values of parameters, mounting arrangements, use of materials, colors, orientations, etc.). For example, elements shown as integrally formed may be constructed of multiple parts or elements show as multiple parts may be integrally formed, the operation of the interfaces may be reversed or otherwise varied, the length or width of the structures and/or members or connector or other elements of the system may be varied, the nature or number of adjustment positions provided between the elements may be varied (e.g. by variations in the number of engagement slots or size of the engagement slots or type of engagement). The order or sequence of any process or method steps may be varied or re-sequenced according to alternative embodiments. Other substitutions, modifications, changes and omissions may be made in the design, operating conditions and arrangement of the various examples of embodiments.

While this invention has been described in conjunction with the examples of embodiments outlined above, various alternatives, modifications, variations, improvements and/or substantial equivalents, whether known or that are or may be presently foreseen, may become apparent to those having at least ordinary skill in the art. Accordingly, the examples of embodiments of the invention, as set forth above, are intended to be illustrative, not limiting.

Claim 1:
An electrochemical cell (<NUM>) comprising:
- a flat positive plate (<NUM>) composed of a positive grid (<NUM>) formed of virgin lead or high purity lead or highly purified secondary lead and a positive battery paste (<NUM>) disposed on the positive grid (<NUM>), the positive battery paste (<NUM>) comprising a lead-containing composition, a positive plate paste vehicle, and a polyvinylsulfonate additive, wherein the virgin lead or high purity lead or highly purified secondary lead is in the range of <NUM>% to <NUM>% lead;
- a flat negative plate (<NUM>) composed of a negative grid (<NUM>) and a negative battery paste (<NUM>) disposed on the negative grid (<NUM>), the negative battery paste (<NUM>) comprising a lead-containing composition and a negative plate paste vehicle;
- an absorbent glass mat (<NUM>) interleaved between the flat positive plate (<NUM>) and the flat negative plate (<NUM>); and
- an electrolyte (<NUM>) in a container (<NUM>) and retained in the absorbent glass mat (<NUM>), the electrolyte (<NUM>) including phosphoric acid, wherein the phosphoric acid is present in the electrolyte (<NUM>) in a range of from <NUM>/L to <NUM>/L.