WO2016087194A2

WO2016087194A2 - Storage battery assembly for a vehicle

Info

Publication number: WO2016087194A2
Application number: PCT/EP2015/076864
Authority: WO
Inventors: Andreas Graefenstein; Markus Beylich; Marcel Mayer
Original assignee: Mann+Hummel Gmbh
Priority date: 2014-12-04
Filing date: 2015-11-17
Publication date: 2016-06-09
Also published as: DE102014018232B3; WO2016087194A3

Abstract

The invention relates to a storage battery assembly (6) for a vehicle, said assembly comprising a metal-air storage battery (1), a treatment device (18) for treating oxygen-rich exit air (A) of the metal-air storage battery (1) and a control device (9), which is coupled to a sensor device (21) for determining the oxygen content in a compartment (19) of the vehicle and which is designed to control a ventilation device (23) in accordance with sensor signals of the sensor device (21), such that exit air (A) is introduced into the compartment (19) when the oxygen content in the compartment (19) lies below a pre-determined set value.

Description

description

Accumulator arrangement for a vehicle

Technical area

The present invention relates to an accumulator arrangement for a vehicle, wherein the accumulator arrangement comprises a metal-air accumulator.

State of the art

Metal-air accumulators are particularly suitable for mobile applications, such as for motor vehicles due to their achievable high energy density. An example of metal-air batteries are lithium-air batteries. Their mode of operation is briefly explained below. During the discharge of the lithium-air battery, a positive lithium ion is released via an electrolyte to a carbon cathode on a lithium anode with the delivery of an electron. At the carbon cathode reacts in a reduction process, the lithium ion with oxygen first to lithium oxide and then to lithium peroxide. For this reduction process to take place, the carbon cathode is coated with a catalyst, highly porous and therefore has a very large surface area. When charging the lithium-air battery, this process turns around. Oxygen is released at the carbon cathode, metallic lithium is deposited at the lithium anode.

US 2012/0040253 A1 describes a method and a system in which the charge air enriched with oxygen exhaust air of a metal-air battery is stored. When discharging the metal-air accumulator this is the stored oxygen-enriched exhaust air supplied again.

Disclosure of the invention

It is therefore an object of the present invention to provide an improved accumulator arrangement.

Accordingly, an accumulator assembly for a vehicle with a metal-air accumulator, a processing device for processing oxygen-enriched exhaust air of the metal-air accumulator and a control device is proposed. The control device is coupled to a sensor device for determining the oxygen content in a space of the vehicle and is configured to actuate a valve device in dependence on sensor signals of the sensor device in such a way. that the exhaust air is introduced into the room when the oxygen content in the room is below a predetermined set point.

As a result, the oxygen released during charging of the metal-air accumulator can be used to improve the air in the room. In particular, a certain excess of oxygen can be set in the space in relation to the environment. By doing so, for example, an improvement in concentration ability and / or responsiveness, delayed fatigue, or easier breathing in a disease of persons in the room can be achieved. By discharging the oxygen-enriched exhaust air from the metal-air battery accumulator, an increase in the concentration of oxygen in the region of the metal-air accumulator or in its immediate surroundings is avoided. As a result, the formation of an ignitable gas mixture is prevented. This increases the reliability of the accumulator assembly.

The metal-air battery preferably has an anode or first electrode made of a metal block and a cathode or second electrode made of mesoporous carbon. Preferably, the metal-air battery is a lithium-air battery. The metal-air battery can also be a silicon-air battery mulator. The accumulator arrangement is particularly suitable for vehicles such as motor vehicles, trucks, motorcycles, aircraft, construction vehicles, rail vehicles and watercraft. In addition, the accumulator arrangement can be used in immobile applications such as in building technology or the like.

In embodiments, the treatment device is configured to filter out particles from the exhaust air. The treatment device may comprise a particle filter. The particle filter is particularly suitable for particle filtration. That is, the particulate filter is preferably configured to mechanically retain particles contained in the exhaust air, such as dust or the like. For particle filtration, the particle filter can comprise a filter medium made of paper and / or plastic. Furthermore, the filter medium may be coated, impregnated and / or provided with a nanofiber layer.

In further embodiments, the treatment device is adapted to chemically filter the exhaust air. The conditioning device may comprise a filter element. which is adapted to purify the exhaust air of noxious gases or undesirable reaction products that arise when unloading the metal-air battery.

In further embodiments, the treatment device is adapted to condition a humidity of the exhaust air. In particular, the treatment device can be set up to condition the air humidity of the exhaust air in such a way that it has a predetermined relative air humidity. For example, the treatment device may be configured to humidify the exhaust air. Further, the treatment device may comprise a filter element which is adapted to extract moisture from the exhaust air. The filter element may comprise a desiccant such as silica beads. The silica beads may be scattered on a filter medium of the filter element and glued to it. Furthermore, the filter medium may be constructed in layers, wherein, for example, between two nonwoven layers, a layer of silica beads may be arranged. Additionally or optionally, the filter medium may comprise an absorber material, in particular a so-called superabsorber, a functionalized membrane or the like.

In further embodiments, the treatment device is adapted to adapt a pressure level of the exhaust air to a pressure level of the room. For this purpose, the processing device may have a pressure control element. The pressure regulating element may be configured to increase or decrease the pressure of the exhaust air. In further embodiments, the treatment device is adapted to add scents to the exhaust air. Furthermore, the treatment device can be configured to deliver concentration-promoting, disinfecting, antibacterial and / or fungicidal substances to the exhaust air.

In further embodiments, a further valve device of the accumulator arrangement can be controlled by the control device such that the exhaust air can be conducted when discharging the lithium-air accumulator into the environment and when loading the lithium-air accumulator into the processing device. The valve device is preferably a multi-way valve. For example, the valve device may be a solenoid valve.

In further embodiments, the accumulator assembly includes a vent control device configured to vent the space in response to sensor signals from the sensor device when the oxygen content in the space is above the predetermined set point. This can prevent too high an oxygen concentration in the room. For example, the ventilation control device be adapted to control an electric window or a ventilation flap.

In further embodiments, the control device is configured to control the valve device in dependence on sensor signals of the sensor device such that the exhaust air is introduced into the environment or into a storage device when the oxygen content in the space is above the predetermined desired value. In the storage device, which may be for example a pressure tank, the oxygen-enriched exhaust air may for example be stored until it is supplied to the metal-air battery when it is discharged. In further embodiments, the accumulator arrangement comprises a filter device upstream of the metal-air accumulator, which is set up to purify supply air of particles and / or noxious gases fed to the metal-air accumulator and / or to condition a humidity of the supply air in this way, that the supply air has a predetermined relative humidity. This prevents clogging or blocking of the mesoporous second electrode of the metal-air accumulator. In particular, the filter device is adapted to filter out harmful gases such as sulfur oxides SO _x , ammonia NH ₃ , nitrogen oxides NO _x , hydrogen sulfide H ₂ S, carbon monoxide CO, carbon dioxide CO ₂ chemically from the supply air. The filter device is preferably also configured to condition the supply air supplied to the metal-air accumulator such that the supply air has a predetermined relative air humidity. In particular, the filter device is adapted to withdraw the supply air, the entire moisture or to ensure a defined and consistent level of humidity.

Further possible implementations of the accumulator arrangement also include not explicitly mentioned combinations of features or embodiments of the accumulator arrangement described above or below with respect to the exemplary embodiments. The skilled person will also add or modify individual aspects as improvements or additions to the respective basic form of the accumulator arrangement. Further embodiments of the accumulator arrangement are the subject matter of the subclaims and the exemplary embodiments of the accumulator arrangement described below. Furthermore, the accumulator arrangement will be explained in more detail by means of embodiments with reference to the attached figures. Brief description of the drawings

Fig. 1 is a schematic sectional view of an embodiment of a metal-air accumulator in a state of charge;

FIG. 2 shows a schematic sectional view of the metal-air accumulator according to FIG. 1 in a discharge state; FIG.

Fig. 3 is a schematic sectional view of another embodiment of a metal-air accumulator in a discharge state;

Fig. 4 is a schematic sectional view of another embodiment of a metal-air accumulator in a discharge state; and Fig. 5 is a schematic view of an embodiment of a storage battery assembly.

In the figures, the same reference numerals designate the same or functionally identical elements, unless indicated otherwise.

Embodiment (s) of the invention

Fig. 1 shows a schematic sectional view of a metal-air accumulator 1 in a state of charge. Fig. 2 shows a schematic sectional view of the metal-air battery 1 in a discharge state. The metal-air accumulator 1 has an anode made of metal, in particular of lithium Li, or first electrode 2 and a cathode or second electrode 3. In the following, only lithium-air batteries 1 will be discussed explicitly. The second electrode 3 is made of mesoporous carbon C and not directly involved in the electrochemical process. Mesoporous solids, as defined by the International Union of Pure and Applied Chemistry (IUPAC), are porous materials with a pore diameter between 2 nm and 50 nm. Carbon C serves as an electrical conductor and terminal, and the mesoporous structure maximizes the surface area Reaction of oxygen 0 ₂ with lithium ions Li ⁺ in the region of the second electrode 3 to facilitate.

The first electrode 2 consists of a block of metallic lithium Li. Alternatively, the first electrode 2 may be made of another metal such as silicon. Between the two electrodes 2, 3 is an electrolyte 4, which depending on the embodiment of the lithium-air battery 1 liquid, in particular water-based, or may be solid. In the latter case, there is a solid-state accumulator. Farther For example, the electrolyte 4 may be an organic liquid that does not react with the lithium Li.

3 shows a schematic sectional view of an embodiment of a lithium-air rechargeable battery 1 with a water-based electrolyte 4. In order to prevent the metallic lithium Li from reacting with the electrolyte 4, a first electrode 2 and the aqueous electrolyte 4 are present Protective layer 5 is provided. Protective layer 5 may be a glass-ceramic layer resting on the metallic lithium Li. For example, the protective layer 5 is a so-called LiSICON layer (LiM ₂ (P0) ₃ ). The protective layer 5 allows the lithium Li to remain stable in the aqueous environment.

4 shows a schematic sectional view of an embodiment of a hybrid lithium-air battery 1. In this case, an organic electrolyte 4 is arranged between the first electrode 2 and the protective layer 5, and an aqueous electrolyte 4 is arranged between the protective layer 5 and the second electrode 3. The basic operating principle in all types of lithium-air batteries 1 is substantially identical. During the discharge (FIGS. 2, 3, 4), a positive lithium ion Li ^{+ is released} via the electrolyte 4 to the second electrode 3 at the first electrode 2, emitting an electron e ^" , where the lithium ion Li ^{+ is released} oxygen 0 ₂ initially lithium oxide Li ₂ 0 and then oxidized to lithium peroxide Li ₂ 0 ₂ the outcome here the following reduction process takes.. 0 ₂ + 4e ^"-> · 2 O ^{2" With} this reduction process to take place, the Therefore, the second electrode 3 is susceptible to contamination with particles such as dust or sand which may clog or block the second electrode 3, and secondly to a second electrode 3 having a catalyst, highly porous and therefore has a very large surface area have noxious gases such as sulfur oxides S _x O _y , ammonia NH ₃ , nitrogen oxides NO _x , hydrogen sulfide H ₂ S, carbon monoxide CO, carbon dioxide CO ₂ and others as catalyst poisons, which could irreversibly damage the second electrode 3 Furthermore, the second electrode 3 is also sensitive to moisture.

In the charge (Fig. 1) of the lithium-air battery 1, this process turns around. At the second electrode 3, oxygen O _{2 is} discharged, at the first electrode 2, metallic lithium Li is deposited. The first electrode 2 is susceptible to moisture because the metallic lithium Li can react violently with water.

5 shows a schematic view of an embodiment of a rechargeable battery Order 6 with a lithium-air battery 1 as previously described. In Fig. 5 signal lines are shown with solid lines and air paths with dashed lines. Air paths can be, for example, air-conducting ducts, pipes or pipes.

The lithium-air accumulator 1 may comprise an accumulator control unit 7, which may be accommodated in a housing of the lithium-air accumulator 1. The accumulator control unit 7 is coupled via a signal line 8 to a control device 9 of the accumulator arrangement 6. The control device 9 can also be designed as a control device.

The lithium-air battery 1 is supplied via an air path 10, the supply air L. Via an air path 1 1 exhaust air A is discharged from the lithium-air battery 1. In the discharge state of the lithium-air battery 1, the reduction process described above takes place. That is, in the discharge state, the exhaust air A is oxygen poorer compared to the supply air L. In the state of charge of the lithium-air battery 1, the exhaust air A is oxygen-rich compared to the supply air L. Both the air path 10 and the air path 1 1 each include a valve means 12, 13. The valve means 12, 13 may be multi-way valves. The valve devices 12, 13 can be controlled by the control device 9. For this purpose, the valve device 12 is coupled by means of a signal line 14 and the valve device 13 by means of a signal line 15 to the control device 9. The first valve device 12 is upstream and the second valve device 13 is positioned downstream of the lithium-air accumulator 1.

The valve device 13 can be controlled with the aid of the control device 9 so that in particular in the discharge state of the lithium-air battery 1, the oxygen-poor exhaust air A is discharged via an air path 1 6 to the environment. Alternatively, the valve device 13 can be controlled so that the, in particular in the state of charge of the lithium-air battery 1 oxygen-enriched, exhaust air A is fed via an air path 17 to a treatment device 18.

The treatment device 18 is configured to treat the exhaust air A so that they can be a room 19 in which people are accommodated, can be supplied. The space 19 may be, for example, a passenger compartment of a vehicle. The processing device 18 is coupled to the control device 9 with the aid of a signal line 20. In or at the space 19, a sensor device 21 is provided which is adapted to determine the air quality in the space 1 9. The sensor device 21 may be an oxygen sensor in order to determine the oxygen content in the space 19. The sensor device 21 is operatively connected to the control device 9 with the aid of a signal line 22.

The processing device 18 may comprise several functionalities for air treatment. In this case, the processing device 18 may have one or more filter elements in order to realize these functionalities.

The treatment device 18 may comprise a particle filter. The particle filter is suitable for particle filtration. That is, the particulate filter is configured to mechanically retain particulates contained in the exhaust air A, such as dust or the like. For particle filtration, the particle filter may comprise a filter medium made of paper and / or plastic. Furthermore, the filter medium can be coated, impregnated and / or provided with a nanofiber layer.

The treatment device 18 may further comprise a filter element, which is adapted to clean the exhaust air A of noxious gases or undesirable reaction products that arise during discharge of the lithium-air battery 1. In particular, the filter element is adapted to chemically filter harmful gases such as sulfur oxides SO _x , ammonia NH ₃ , nitrogen oxides NO _x , hydrogen sulfide H ₂ S, carbon monoxide CO, carbon dioxide CO ₂ from the exhaust air A. The filter element may have, for example, activated carbon for chemical filtration. Furthermore, the filter element can comprise potassium carbonate K ₂ CO ₃ and / or calcium hydroxide Ca (OH) ₂ , which reacts chemically with acidic pollutants such as sulfur oxides SO _x or hydrogen sulfide H ₂ S in order to neutralize these noxious gases.

The treatment device 18 may also comprise a filter element which is adapted to extract moisture from the exhaust air A. The filter element may comprise a desiccant such as silica beads. The silica beads may be scattered on a filter medium of the filter element and glued to it. Furthermore, the filter medium may be constructed in layers, wherein, for example, between two nonwoven layers, a layer of silica beads may be arranged. Additionally or optionally, the filter medium may comprise an absorber material, in particular a so-called superabsorber, a functionalized membrane or the like. Furthermore, the treatment device 18 can also be set up to humidify the exhaust air A.

The processing device 18 may further be adapted to adjust the pressure level, that is, to increase or decrease the pressure if necessary, in order to achieve an adaptation to the pressure prevailing in the space 19. The processing Device 18 may also be adapted to enrich the exhaust air A with additives such as fragrances.

Downstream of the treatment device 18, a third or further valve device 23 is provided, which is connected to the processing device 18 via an air path 24. The valve device 23 is coupled to the control device 9 with the aid of a signal line 25. The valve device 23 is preferably a multi-way valve. The valve device 23 is set up to discharge the exhaust air A either via an air path 26 into the environment or via an air path 27 to the space 19. The space 19 may be connected to the valve device 12 with an optional air path 28.

The accumulator arrangement 6 can have an optional ventilation control device 29, which is coupled to the control device 9 via a signal line 30. The vent control device 29 may also be a control device. The ventilation control device 29 may be configured to control the ventilation of the space 19, for example by opening and closing windows or ventilation openings.

The lithium-air accumulator 1 may be preceded by a filter device 31, which is adapted to process the supply air L. In particular, the filter device 31 may be configured to purify the supply air L of particles. As a result, an addition or blocking of the mesoporous second electrode 3 is prevented.

Furthermore, the filter device 31 is also adapted to filter out harmful gases contained in the supply air L. In particular, the filter device 31, like the treatment device 18, is adapted to chemically filter harmful gases such as sulfur oxides SO _x , ammonia NH ₃ , nitrogen oxides NO _x , hydrogen sulfide H ₂ S, carbon monoxide CO, carbon dioxide CO ₂ from the supply air L. These noxious gases can act as catalyst poisons that can permanently damage the catalyst provided on the second electrode 3. The filter device 31 may have, for example, potassium carbonate K ₂ CO ₃ , calcium hydroxide Ca (OH) ₂ and / or activated carbon for chemical filtering. As a result, the catalyst effect persists permanently. The filter device 31 is preferably also configured to condition the supply air L supplied to the lithium-air accumulator 1 in such a way that the supply air L has a predetermined relative air humidity. In particular, the filter device 31 is adapted to extract the supply air L, the entire moisture. This will be a Reaction of the metallic lithium Li of the first electrode 2 prevented with water. When used for other types of metal-air batteries such as silicon-air batteries, the filter device 31 may be configured to provide a defined and consistent level of humidity. The functionality of the accumulator assembly 6 will be briefly explained below. During the discharge of the lithium-air battery 1, the treated supply air L is supplied to it. The valve device 13 is switched so that the oxygen-depleted exhaust air A is discharged via the air path 1 6 in the environment.

When charging the lithium-air accumulator 1, in which at the second electrode 3 oxygen 0 _{2 is} discharged, the second valve device 13 is controlled by the control device 9 so that the exhaust air A is supplied via the air path 17 of the processing device 18. In the treatment device 18, the exhaust air A, as described above, processed. Depending on how high the determined by the controller 9 by means of the sensor device 21 oxygen content in the space 19, the third valve device 23 is either driven so that the exhaust air A is discharged via the air path 26 to the environment or that the exhaust air A is passed via the air path 27 into the space 19. If the determined oxygen content in the space 19 is above a predetermined desired value, the exhaust air A is discharged to the environment. Alternatively, the oxygen-enriched exhaust air A can be stored with the aid of a storage device in order, for example, to be fed back to the lithium-air accumulator 1 when it is being unloaded. The storage device may be a pressure tank. If the determined oxygen content in the space 19 is below the desired value, the oxygen-enriched exhaust air A is conducted into the space 19. Here, the oxygen content of the air in the space 19 may be higher than in the environment. In this way, for example, the ability of a driver to concentrate can be improved.

If the oxygen content in the space 19 is too high, the oxygen content can be lowered very rapidly by ventilating the space 19 with the aid of the ventilation control device 29. The air contained in the space 19 can continue to be supplied via the optional air path 28 of the first valve device 12 as a supply air L for the lithium-air battery 1 Akku-.

Claims

claims

1 . Accumulator assembly (6) for a vehicle, comprising a metal-air accumulator (1), a treatment device (18) for processing oxygen-enriched exhaust air (A) of the metal-air accumulator (1) and a control device (9), which is coupled to a sensor device (21) for determining the oxygen content in a space (19) of the vehicle, and which is set up to control a valve device (23) in dependence on sensor signals of the sensor device (21) in such a way that the exhaust air (A) is introduced into the space (19) when the oxygen content in the space (19) is below a predetermined set point.

Second accumulator assembly according to claim 1, wherein the processing device (18) is adapted to filter out particles from the exhaust air (A).

3. Accumulator assembly according to claim 1 or 2, wherein the processing device (18) is adapted to chemically filter the exhaust air (A).

4. Accumulator arrangement according to one of claims 1-3, wherein the treatment device (18) is adapted to a humidity of the exhaust air (A) to konditi- onions.

5. Accumulator arrangement according to one of claims 1 - 4, wherein the processing device (18) is adapted to adjust a pressure level of the exhaust air (A) to a pressure level of the space (19).

6. Accumulator arrangement according to one of claims 1-5, wherein the treatment device (18) is adapted to the exhaust air (A) add fragrances.

7. Accumulator arrangement according to one of claims 1 - 6, wherein a further valve means (13) of the accumulator assembly (6) by the control device (9) is controlled so that the exhaust air (A) during discharge of the lithium-air Accumulator (1) in the environment and when loading the lithium-air battery (1) in the processing device (18) is conductive.

8. Accumulator device according to one of claims 1-7, wherein the accumulator arrangement (6) comprises a ventilation control device (29) which is adapted to ventilate the space (19) in response to sensor signals of the sensor device when the Oxygen content in the space (19) is above the predetermined setpoint.

9. Accumulator arrangement according to one of claims 1-8, wherein the control device (9) is adapted to control in response to sensor signals of the sensor device (21), the valve device (23) such that the exhaust air (A) in the environment or is introduced into a storage device when the oxygen content in the space (19) is above the predetermined set point.

10. Accumulator arrangement according to one of claims 1 - 9, wherein the accumulator arrangement (6) comprises a metal-air accumulator (1) upstream filter means (31) which is adapted to the metal-air accumulator ( 1) supplied supply air (L) of particles and / or noxious gases to clean and / or a humidity of the supply air (L) to condition so that the supply air (L) has a predetermined relative humidity.