JP6324007B2 - Energy storage device, manufacturing method thereof, and detection means - Google Patents

Description

  The present invention relates to an energy store. The invention particularly relates to lithium-ion batteries.

Prior art Lithium-ion batteries are widely used as energy stores in many everyday applications. Lithium-ion-batteries are used, for example, in computers such as laptops, mobile phones, smartphones and other applications. The above-described battery is also advantageous in electrification of vehicles such as automobiles that are being strongly propelled today.

  Different options are known in order to avoid the hazards caused by energy stores such as lithium-ion batteries. These options are used, for example, to avoid the danger that the energy store may overheat, burn, or release dangerous gases or dusts in the event of a maritime accident. With all the appropriate safety measures, an energy store such as a lithium-ion battery can be used without significant danger.

  From publication DE 3818694 Al a battery pack for display and goods is known. In such a battery pack, since the battery poles can be connected by electrical contacts, the magnitude of the battery voltage can be indicated when a current flows. However, such a battery pack is not suitable for obtaining safety.

DE 3818694 Al

  An object of the present invention is to provide an energy accumulator which can detect even a very small damage of a battery casing with certainty and high reliability and which is advantageous in a simple and cost-effective manner. Is to provide a method of manufacturing the energy store and a method of using the detection means to manufacture the energy store.

  According to claim 1 of the present invention, an object of the above energy storage is an energy storage, in particular a lithium-ion battery, including a cell space, which comprises an anode, a cathode, and In an energy storage device in which an electrolyte disposed between the anode and the cathode is disposed, the cell space is at least partially isolated from the external environment by a casing, and the casing is the casing during operation of the energy storage device. This is solved by configuring an energy storage device characterized in that it has detection means for detecting at least one component present in it or the reaction product of this component.

  According to claim 8 of the present invention, there is provided a detection means for detecting at least one component or a reaction product of this component present in the casing during operation of the energy store. It is solved by a method of manufacturing an energy store, comprising the method steps of depositing an energy store on the casing of the energy store.

1 is a schematic diagram of one embodiment of an energy store according to the present invention. FIG. FIG. 3 is a schematic diagram of another embodiment of an energy store according to the present invention.

  The present invention is directed to an energy storage, such as a lithium-ion battery, which has a cell space that includes an anode, a cathode, and An electrolyte is disposed between the anode and the cathode. The cell space is at least partially isolated from the external environment by a casing, the casing having detection means for detecting at least one component in the casing or a reaction product of this component during operation of the energy accumulator. .

  In the present invention, the energy storage can be an arbitrary battery. For example, the energy storage can be a secondary battery, in particular a secondary battery, ie a rechargeable storage battery. Here, the battery can be one galvanic element or a plurality of galvanic elements connected to each other. For example, the energy store may include a lithium-ion battery. Lithium-ion-battery can be understood, for example, as an energy store in which at least part of the electrochemical process during the charging or discharging process is based on lithium ions.

  Further, in the present invention, a cell space can be understood as a space where an anode, a cathode and an electrolyte are present or arranged. Therefore, the cell space is a space where an electrochemical process that proceeds with respect to the charging or discharging process of the energy storage is performed. Furthermore, the casing surrounding the cell space can directly surround the cell space, i.e. purely by way of example as a cell space wall, or indirectly surround the cell space. In the latter case, the casing can be configured as another casing that surrounds, for example, a casing that directly surrounds the cell space.

  Furthermore, the external environment can in particular be an energy storage or an atmosphere surrounding the casing, i.e. in particular the air surrounding the energy storage.

  Furthermore, the detection means is any means capable of detecting a component directly or indirectly. For example, the detection means can be an electronic sensor or can be a substance that can, for example, chemically react with the component to be detected. Here, this component can be detected, for example, by a sudden discoloration of the detection means, in particular by a sudden discoloration of the detection means, which is substantially irreversible under the normal operating conditions of the energy storage. . In general, the detection means can visually display, for example, a component to be detected.

  Furthermore, the detection means described above can sense or sort out components such as substances present in the casing during normal and desired operation of the energy store. At this time, the detection means can directly sort out the components as described above, or can directly detect the components. Furthermore, the detection stage can select the reaction products of the above components, and in particular, can select the products formed by the reaction of these components in the atmosphere outside the casing or in the external environment. In the last case, the detection means detects the above components indirectly.

  With such an energy accumulator, it is possible to detect casing damage early and reliably, which can significantly reduce the spread or expansion of the damage and, for example, the risk to the user of the energy accumulator. Or it can even be completely blocked. This allows the energy storage device of the present invention to be operated particularly safely.

  Specifically, a casing that can be used or configured as a battery cover detects at least one component present in the casing or the reaction product of this component during operation of the energy accumulator. Therefore, the leakage of such a component can be directly detected. Depending on the detection means chosen, very small concentrations can be reliably identified, so that not only relatively large damage can be detected directly, but also very slight leaks such as micro-perforations or micro-cracks can be directly identified. Thereby, even damage that cannot be identified with the naked eye, for example, can be identified.

  This allows it to react to even very small damages, so that it can only stop or stop the material leakage or damage expansion, so that a peripheral configuration such as another energy storage, for example. Damage to the member can be reliably prevented. Therefore, in some cases, the expected repair cost can be reduced to a minimum.

  In addition, it is possible to immediately terminate a situation in which a substance such as a gas or a liquid continuously leaks out of the energy store, for example to minimize or completely prevent the user's risk. Can do. This is especially true for substances present in the energy accumulator, or for some of its reaction products and decomposition products such as air or moisture in the air, with personnel in the immediate vicinity of the operator or energy accumulator. Can be particularly advantageous since it can be a harmful substance that can be endangered. Thereby, according to the present invention, it is possible to realize protection of personnel in contact with the energy accumulator. Furthermore, the danger of critical situations for safety such as thermal runaway can be greatly reduced.

  Thus, the energy storage device described above is able to ensure a very simple and cost-effective and particularly safe operation by directly and quickly detecting even very small damages of the casing. This can reduce or completely prevent damage around the energy accumulator and reduce or eliminate situations that endanger personnel. Therefore, the energy storage including the above-mentioned detection means is, for example, an indicator for leakage or damage, and is therefore an advantageous means for quality control or quality assurance of the energy storage. Here, as described above, both the quality assurance at the end user and the quality assurance at the manufacturer can be improved. This is because the detection means described above can identify leaks immediately after the energy accumulator is manufactured and before it is sold, thereby enabling a screening step in this regard.

  In addition, defective batteries have the risk of thermal runaway in some cases, but this risk can also be prevented by the energy store.

  Thus, the energy store described above can primarily counter performance degradation and also reduce potential risks that can be caused by a damaged energy store. Further, energy stores that are leaking or likely to leak after manufacture or during operation can be immediately identified and removed.

  Within the frame of one embodiment, the detection means described above can be applied to the outer surface of the casing in the form of a coating. This is a particularly simple and cost-effective option for enabling the detection means to be applied to the casing. This embodiment is particularly advantageous for substances which can be used as detection means, for example by being able to react chemically with the component to be detected or the reaction product of this component. Such a detection means can be, for example, a coating such as lacquer and can thus be applied particularly simply to the casing. In addition, the coating can particularly advantageously cover the large surface of the casing and is basically inaccessible to the position of the casing and / or a position that is known to be critical as known. Can also be monitored.

  Within the frame of another embodiment, it is possible to completely coat the casing by means of detection. In particular, this embodiment can be advantageous not only in that it can basically detect only leakage of a substance such as a gas from the casing, but also in that it can directly detect the leaked position and thus the damaged position of the casing. is there. In this way, for example, it is possible to take measures for repair directly and cost-effectively without checking the energy accumulator in detail. Furthermore, the exchange can be carried out particularly quickly and advantageously. Furthermore, if damage is detected, it can be easily checked whether there is only this damage, or whether there is another failure that must be repaired or replaced as well. In the present invention, it may mean that the above casing is completely coated with the detecting means, for example, the outer wall of the casing is coated with the detecting means and used for fixing a lead wire or energy storage extending from the casing. The individual positions, such as fixing means, are not particularly coated for technical reasons.

  Within the frame of another embodiment, the detection means described above can be arranged at the connection point of the casing. For example, the detection means can be arranged only at the connection location of the casing or exclusively at the connection location. In this embodiment in particular, particularly weak points of the casing or energy storage can be monitored for damages such as microcracks or microperforations. In this case, it is possible to dispense with a large-area coating or a plurality of sensors that completely cover the casing, which makes it possible in this embodiment to make the energy storage particularly cost-effective. In the present invention, the connecting part of the casing means, in particular, an opening for a conducting wire, a weld seam, a connecting part of individual casing components or the like.

  Within the framework of another embodiment, the above-described detection means can detect the electrolyte component or the reaction product of the electrolyte component. This embodiment can be particularly advantageous because the electrolyte can have volatile or liquid components in particular, or can have components that can react with the components described above. This is particularly possible in electrolytes where such components can cause damage or can be toxic to humans. Furthermore, in particular, the electrolyte can be present in most or a wide area of the energy storage, so that the energy storage can be reliably and reliably detected, in particular by means of detecting the electrolyte or its components. .

Within another embodiment, the detection means can be selected from the group consisting of zirconium-alizarin-S and iron thiocyanate (Fe (SCN) ₃ ). Such detection means can detect the presence of leaks reliably and reliably, especially with high sensitivity and sorting capability. For example, the above detection means can detect hydrofluoric acid with high reliability. This can be particularly advantageous for the case of a purely exemplary lithium-ion battery as an energy store. This is because, for a purely exemplary lithium-ion-battery case, the above electrolyte can have lithium hexafluorophosphate (LiPF ₆ ) as the supporting electrolyte. When this supporting electrolyte comes into contact with surrounding moisture or moisture in the air at a leak point or the like, this supporting electrolyte can be decomposed into, for example, hydrofluoric acid. This can be caused, for example, by the leakage of the supporting electrolyte and the reaction outside the casing, or by air or moisture in the air entering the casing and not reacting in the casing or near the cell space. Can also happen. As the amount of hydrofluoric acid formed increases, the aging of the energy accumulator is accelerated, which in turn leads to performance degradation. Furthermore, the formation and leakage described above can result in potential hazards due to toxicity. For this reason, in particular a detection means that can selectively detect the presence of hydrofluoric acid can be advantageous. Here, in particular, the detection means as a coating for sensing hydrofluoric acid on the casing of the energy storage device is based on the presence of hydrofluoric acid and thus the presence of damage such as micro-perforations. It can be indirectly shown optically or visually.

In particular, zirconium-alizarin-S as the detection means described above chemically reacts with hydrofluoric acid, which becomes indirectly visible to the eye by a substantially irreversible rapid discoloration. In detail, for example, zirconium-alizarin-S, which itself contains a purple lacquer, can be decolorized and the corresponding part can turn yellow-red. For the crimson iron thiocyanate complex, it can be decolorized, for example by the formation of the complex Fe [F] ₆ in a solution of hydrofluoric acid.

  Thereby, for example, an expensive analysis unit or sensor can be omitted in this embodiment. Rather, it is possible to reliably and reliably detect damage by simply coating the casing. As a result, the energy accumulator of this embodiment can be produced particularly cost-effectively and simply.

  The above embodiment is a particularly advantageous example of a visually perceptible abrupt discoloration, which demonstrates the presence of hydrofluoric acid. This makes it possible to determine the location of defective energy stores and damage by simply visually checking one or more energy stores, simply, quickly and with high reliability.

Within the frame of another embodiment, the detection means comprises an electrode that senses a component present in the casing or the reaction product of this component during operation of the energy storage. For example, the detection means may have an electrode that senses fluoride. Therefore, in this embodiment, the presence of hydrofluoric acid can be detected by voltage detection, which can likewise enable accurate and reliable detection of leakage. For example, such a fluoride sensing electrode may be composed of LaF ₃ / EuF ₂ or may contain these materials.

  For further technical features and advantages of the energy store according to the invention, reference is made to the method according to the invention, the method of use according to the invention, the drawings and the description relating to the description of the drawings.

  The present invention is further directed to a method of manufacturing an energy storage, such as a lithium-ion battery, which includes at least one component present in the casing during operation of the energy storage or A method step is included in which detection means for detecting the reaction product of this component is applied to the casing of the energy storage.

  The method according to the invention makes it possible to provide an energy accumulator in a particularly simple and cost-effective manner, wherein the energy accumulator can reliably and reliably detect even very small damage to the battery casing. Can do. This prevents both relatively large damage to the energy store itself, or relatively large damage to other components in the immediate vicinity of the energy store, such as another energy store. Or it can be at least significantly reduced. Furthermore, it is possible to prevent the material from leaking continuously from the energy storage, thereby greatly reducing or completely preventing the situation that directly poses a danger to the operator of the energy storage.

  Within the frame of one embodiment, the detection means is applied to the casing in the form of a coating. This is a particularly simple and cost-effective option for enabling the detection means to be fixed or attached to the casing. Furthermore, the thickness and spread of the coating can be controlled in a simple and predetermined manner.

  For further technical features and advantages of the method according to the invention, reference is made to the energy storage according to the invention, the method of use according to the invention, the drawings and the description relating to the description of the drawings.

  The invention further detects at least one component or the reaction product of this component present in the casing of the energy store during operation of the energy store to produce an energy store, such as a lithium-ion battery. It is intended for a method of using the detection means to do so.

  By using or depositing detection means on the energy storage, in particular on the outer surface of the casing of the energy storage, extremely small damage to the energy storage is particularly simple and cost-effective and reliable and reliable. Even it can be detected. This can first reduce or prevent damage to components located near the energy accumulator. Furthermore, the situation where the operator of the energy storage device is exposed to danger can be greatly reduced or completely prevented.

  For further technical features and advantages of the method of use according to the invention, reference is made to the energy accumulator according to the invention, the method according to the invention, the drawings and the description relating to the description of the drawings.

  Further advantages and advantageous embodiments of the subject of the invention are specifically illustrated by means of examples and drawings and are described below. It should be noted that these examples and drawings are illustrative in nature and are not intended to limit the invention in any way.

  FIG. 1 shows a schematic diagram of an energy storage 10 according to the present invention. Such an energy storage 10 can be basically any type of energy storage, for example a battery such as a rechargeable storage. For example, the energy storage 10 can be a lithium-ion battery. Possible application areas are electrically powered vehicles, computers such as laptops, mobile phones, smartphones, electrical tools and other applications.

  Such energy storage 10 includes a cell space in which an anode, a cathode, and an electrolyte disposed between the anode and the cathode are disposed. Further, as is well known, a separator is disposed between the anode and the cathode.

The anode and cathode can be constructed in a manner known per se for energy storage, essentially as is known per se. For a purely exemplary lithium-ion-battery case, the anode can be an electrode that contains metallic lithium or can intercalate lithium. The cathode can illustratively comprise NMC or lithium cobalt oxide (LiCoO ₂ ). The cathode material is optionally provided in a binder such as polyvinylidene fluoride (PVDF) that contains a conductive additive such as a conductive carbon compound such as graphite. The electrolyte may include a solvent in which one or more conductive salts are dissolved. For example, an aprotic solvent such as ethylene carbonate, propylene carbonate, dimethyl carbonate or diethyl carbonate can be used. Furthermore, lithium hexafluorophosphate (LiPF ₆ = lithium hexafluorophosphate) can be used as the conductive salt.

  Furthermore, a separator is arranged in a known manner between the anode and the cathode, in order to spatially separate the anode and the cathode, in particular to prevent short circuits. This separator can for example consist of a porous plastic sheet, a graph fiber fabric, or in particular a porous ceramic material such as a ceramic fabric. Here, the above-described electrolyte can be disposed, for example, in the separator or in the hole of the separator.

  The cell space in which the anode, cathode, separator, and electrolyte are disposed is at least partially separated from the surroundings by the casing 12. The casing 12 can be made of any material. For example, the casing 12 can be a rigid casing, i.e. a casing that does not change shape, or it can be an elastic casing 12 made of, for example, plastic plastic. According to FIG. 1, conductors 14, 16 protrude from the casing 12 for electrical contact and connection to the energy accumulator to extract electrical energy.

  The casing 12 further comprises detection means 18 for detecting at least one component present in the casing 12 or the reaction product of this component during operation of the energy storage 10. According to FIG. 1, the detection means 18 is applied to the outer surface of the casing 12 in the form of a coating, for example a lacquer coating. Basically, the detection means 18 can be arranged only at the connection location of the casing 12. However, FIG. 1 shows that the casing 12 is completely coated by the detection means 18.

  Furthermore, the detection means 18 can detect the electrolyte component or the reaction product of the electrolyte component. For this purpose, the detection means described above may comprise, for example, zirconium-alizarin-S or iron thiocyanate, for example as a lacquer coating.

If the casing 12 is damaged or if the casing 12 has microcracks, for example, a supporting electrolyte such as LiPF ₆ of the above electrolyte can react with moisture in the air to become hydrofluoric acid. When this hydrofluoric acid comes into contact with the detection means, this is directly visible by a sudden change in color. This is indicated by the color changing portion 20 in FIG.

  Therefore, the energy storage device 10 according to the present invention provides at least one component present in the casing 12 during the operation of the energy storage device 10 or a detection means 18 for detecting a reaction product of this component on the casing 12 of the energy storage device 10. It can be produced by a method known per se, which further comprises a method step of applying to the substrate.

  FIG. 2 shows another embodiment of an energy storage 10 according to the present invention. The energy store 10 of FIG. 2 substantially corresponds to the energy store 10 of FIG. The difference is that the energy storage 10 of FIG. 2 is configured as a wound cell. In FIG. 2, the detection of a leak can also be identified, and this leak can be identified indirectly by a sudden color change 20.

  It will be apparent to those skilled in the art that the above description of the energy storage device 10 of the present invention is merely illustrative and is not limited by the embodiments described above.

  DESCRIPTION OF SYMBOLS 10 Energy storage, 12 Casing, 14,16 Conductor, 18 Detection means, 20 Color change part

Claims (18)

An energy store including cell space,
In the energy accumulator, in which the cell space is arranged with an anode, a cathode, and an electrolyte arranged between the anode and the cathode,
The cell space is at least partially isolated from the external environment by a casing (12);
It said casing (12), possess the casing at least one component or detecting means for detecting a reaction product of the components present in (12) (18) during operation of the energy storage device (10),
The detection means (18) has an electrode for sensing a component present in the casing (12) during operation of the energy storage (10) or sensing a reaction product of the component.
An energy storage (10) characterized in that. The energy store according to claim 1, wherein
The detection means (18) is deposited on the outer surface of the casing (12) in the form of a coating,
An energy storage (10) characterized in that. The energy store according to claim 2, wherein
The casing (12) is completely coated by the detection means (18);
An energy storage (10) characterized in that. The energy store according to claim 1 or 2,
The detection means (18) is arranged at a connection location of the casing (12).
An energy storage (10) characterized in that. In the energy storage device according to any one of claims 1 to 4,
The detection means (18) can detect an electrolyte component or a reactive product of the electrolyte component,
An energy storage (10) characterized in that. The energy accumulator of claim 5, wherein
The detection means is selected from the group consisting of zirconium-alizarin-S and iron thiocyanate;
An energy storage (10) characterized in that. An energy store including cell space,
In the energy accumulator, in which the cell space is arranged with an anode, a cathode, and an electrolyte arranged between the anode and the cathode,
The cell space is at least partially isolated from the external environment by a casing (12);
The casing (12) has detection means (18) for detecting at least one component present in the casing (12) or a reaction product of the component when the energy accumulator (10) is operated.
The detection means (18) can detect an electrolyte component or a reactive product of the electrolyte component,
The detection means (18) is selected from the group consisting of zirconium-alizarin-S and iron thiocyanate;
An energy storage (10) characterized in that. The energy accumulator of claim 7.
The detection means (18) is deposited on the outer surface of the casing (12) in the form of a coating,
An energy storage (10) characterized in that. The energy store according to claim 8, wherein
The casing (12) is completely coated by the detection means (18);
An energy storage (10) characterized in that. 9. An energy accumulator according to claim 7 or 8,
The detection means (18) is arranged at a connection location of the casing (12).
An energy storage (10) characterized in that. The energy storage device according to any one of claims 1 to 10 ,
The energy store (10) is a lithium-ion battery.
An energy storage (10) characterized in that. A method of manufacturing an energy accumulator (10) comprising a cell space comprising:
In the cell space, an anode, a cathode, and an electrolyte arranged between the anode and the cathode are arranged,
In the method of manufacturing an energy storage (10), the cell space is at least partially isolated from the external environment by a casing (12).
Detection means (18) for detecting at least one component present in the casing (12) or a reaction product of the component during operation of the energy storage (10) is provided in the casing of the energy storage (10). viewing including the step of depositing,
The detection means (18) has an electrode for sensing a component present in the casing (12) during operation of the energy storage (10) or sensing a reaction product of the component.
A method of manufacturing an energy storage (10), characterized in that A method of manufacturing an energy accumulator (10) comprising a cell space comprising:
In the cell space, an anode, a cathode, and an electrolyte arranged between the anode and the cathode are arranged,
In the method of manufacturing an energy storage (10), the cell space is at least partially isolated from the external environment by a casing (12).
Detection means (18) for detecting at least one component present in the casing (12) or a reaction product of the component during operation of the energy storage (10) is provided in the casing of the energy storage (10). Including the step of depositing,
The detection means (18) can detect an electrolyte component or a reactive product of the electrolyte component,
The detection means (18) is selected from the group consisting of zirconium-alizarin-S and iron thiocyanate;
A method of manufacturing an energy storage (10), characterized in that The method according to claim 12 or 13 , wherein:
Applying said detection means (18) to said casing (12) in the form of a coating;
A method characterized by that. 15. The method according to any one of claims 12 to 14 , wherein
The energy store (10) is a lithium-ion battery.
A method characterized by that. An energy storage (including an anode, a cathode, and a cell space in which an electrolyte disposed between the anode and the cathode is disposed, the cell space being at least partially isolated from the external environment by a casing (12). In the detection means (18) used in 10)
It said detecting means (18) detects the reaction product of at least one component or the components present in the casing (12) of the energy accumulator (10) during operation of the energy storage device,
The detection means (18) has an electrode for sensing a component present in the casing (12) during operation of the energy storage (10) or sensing a reaction product of the component.
Detection means (18) characterized by the above. An energy storage (including an anode, a cathode, and a cell space in which an electrolyte disposed between the anode and the cathode is disposed, the cell space being at least partially isolated from the external environment by a casing (12). In the detection means (18) used in 10)
The detection means (18) detects at least one component or a reaction product of the component present in the casing (12) of the energy store (10) during operation of the energy store,
The detection means (18) can detect an electrolyte component or a reactive product of the electrolyte component,
The detection means (18) is selected from the group consisting of zirconium-alizarin-S and iron thiocyanate;
Detection means (18) characterized by the above. 18. Detection means (18) according to claim 16 or 17 ,
The energy store (10) is a lithium-ion battery.
Detection means (18) characterized by the above.

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