WO2016113278A1 - Electrochemical battery comprising an electronic module inside the casing - Google Patents

Electrochemical battery comprising an electronic module inside the casing Download PDF

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Publication number
WO2016113278A1
WO2016113278A1 PCT/EP2016/050518 EP2016050518W WO2016113278A1 WO 2016113278 A1 WO2016113278 A1 WO 2016113278A1 EP 2016050518 W EP2016050518 W EP 2016050518W WO 2016113278 A1 WO2016113278 A1 WO 2016113278A1
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WO
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Prior art keywords
housing
battery
electrochemical
data
accumulator
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PCT/EP2016/050518
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French (fr)
Inventor
Olivier Masson
Yvan Reynier
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Commissariat A L'energie Atomique Et Aux Energies Alternatives
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/42Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/48Accumulators combined with arrangements for measuring, testing or indicating condition, e.g. level or density of the electrolyte
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/42Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/425Structural combination with electronic components, e.g. electronic circuits integrated to the outside of the casing
    • H01M10/4257Smart batteries, e.g. electronic circuits inside the housing of the cells or batteries
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/42Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/425Structural combination with electronic components, e.g. electronic circuits integrated to the outside of the casing
    • H01M2010/4278Systems for data transfer from batteries, e.g. transfer of battery parameters to a controller, data transferred between battery controller and main controller

Abstract

The invention relates to an electrochemical battery (1) comprising at least: an electrochemical cell made up of at least one anode and one cathode on either side of an electrolyte, a first casing (6) in which the electrochemical cell(s) are sealed, at least two current output terminals (2, 4), each connected to one or the other of the anode(s) and the cathode(s), a second casing (7) that is attached to the inside of the first casing, a sealed confined space (70) being defined therein, an electronic module (72) arranged in said sealed confined space (70), the electronic module (72) comprising at least: a memory, a communication module that is suitable for receiving and/or transmitting data from and/or to the outside of the first casing, a processor, a processor that is suitable for receiving and/or transmitting at least data from and/or to the communication module, the electronic module being electrically powered by the electrochemical cell(s).

Description

ELECTROCHEMICAL BATTERY WITH ELECTRONIC MODULE

INTERNAL HOUSING

Technical area

The present invention relates to the field of electrochemical batteries.

The invention relates in particular to smart electrochemical accumulators, that is to say having a single associated electronics, an element for authentication of the battery and sensors for determining the pressure, temperature, current, and state of charge and health and can communicate data through a communication module.

The invention relates more particularly to communication methods of such data between a smart battery and another battery, or between an intelligent battery and the control electronics of a pack battery or a battery control system batteries (in English, "Battery Management System" acronym BMS).

The invention aims to improve the current batteries in protecting users of accumulators not fulfilling the security requirements and therefore potentially dangerous. It also seeks to allow, via sensors and an electronic module, the measurement and calculation of various parameters such as temperature, the internal pressure of the electrochemical cell, the current at the terminals of the battery, the health status , the state of charge, the actual maximum load of an accumulator, and allowing a simplified communication of data of a battery to an external entity.

BACKGROUND

Li-ion battery manufacturers worldwide market for about twenty years of the cells (with a historically early marketing initiated by SONY company in 1991 to power laptops), in a variety of sizes and forms, the elements being sized according to the intended application. The objective of the cell manufacturers is to increase the autonomy (energy) cells, while increasing their lifespan (number of cycles) and their lightness. But to have a lasting technology and deployed on all markets related to mobility and energy storage, battery reliability is a matter of first order.

For example, in 2006 the company SONY has faced a huge problem of reliability of their batteries. A plane caught fire shortly before landing. The survey privileged as cause a fire starting in batteries produced by Sony and for the power supply of equipment on board the aircraft.

In addition, with the spread of certain technologies in all shipping energy systems, such as lithium-ion batteries in mobile phones for example, battery replacement markets grow increasingly. These replacement markets are often driven by cost, the benefit of low cost manufacturing (low-cost) that do not necessarily include all the subtleties of the original product designs ensure high security. For example, sometimes the phones or computers catch fire spontaneously due to replace the original battery with a low-cost replacement battery.

There are already a number of publications or patents relating to optimization of onboard energy storage batteries and electrochemical sensors and safety device systems to prevent internal pressures to an accumulator that can be dangerous and compromise sealing thereof.

Among the key points discussed include the knowledge of the state of charge (in English "State of Charge", and in the following text referred to by the acronym SOC), health status (in English "State of Health, "and in the following text referred to by the acronym SOH) or security-related condition such electrochemical batteries. The SOC indicates the energy available in a battery before possible recharging. The SOH lets you know how long a battery will be used with specific performance. The security status can predict situations where inopportune events or accidents can happen (short circuit or pressure, for example).

The SOC and SOH of a storage cell can not be measured directly and is calculated or estimated by various methods from other measurable quantities such as the current at the terminals of the accumulator, the internal pressure in the accumulator, the temperature, the voltage of the battery output terminals or the age thereof.

Knowledge of physical quantities within the electrochemical cell at a time t, but also throughout the life of the battery is a key factor in the control and management of the use of it. This also helps to predict and prevent the case SAMPLE accidents in case of anomaly. Among the technical solutions proposed to determine the load conditions, health or safety of electrochemical batteries, there are solutions that are to know the internal pressure of the cell. Indeed, the knowledge of the internal pressure of a cell, either at a time t, is integrated in a clean history to this accumulator, allows for many of the component (electrode or electrolyte) to estimate one or more states mentioned above.

For controlling the lifetime, the temperature being an element of the first order in the estimation thereof, the integration of a temperature sensor inside the same accumulator shows its interest.

In addition, a system for reliably identifying the authenticity of the battery used could prevent the use of lower-quality batteries in equipment.

The European patent applications EP 2461172 and EP 2224574 Al Al describe a method and a battery detection system complies with the original batteries that records the characteristics including current of a battery connected to a mobile device and compared to characteristics current already registered to determine if the battery is consistent or not.

Patent Application WO 2007/001129 Al discloses a battery identification system. This identification system comprises an antenna and a printed circuit. The assembly is located outside the cell housing puisqu'intégré in an assembly forming a casing with cap of the battery.

Patent application US 2011/0309995 discloses an accumulator arranged in a sealed housing. The accumulator is connected to a circuit capable of storing data and a loop type antenna. The printed circuit and the loop antenna are arranged outside the housing and can be operated according to the RFID protocol "radio frequency identification" (in the following text, we will use the acronym RFID).

The patent application FR2953044 Al discloses a battery pack with two identification systems. A first system is attached to the outside of the casing containing an electrochemical cell in a protective layer and a second system is fixed on the protective layer. Systems are for instance chips, which may include storing data, such as an identifier of the cell. Patent application US 2005/0035738 discloses a battery pack-verification system having a temperature sensor and a read-only memory comprising a specific identification number to the pack battery.

Patent application US 2003/0102842 describes an identification system comprising a temperature sensor that triggers the stopping of the battery if it exceeds a given value and an external identification chip to electrochemical battery casings.

U.S. Patent 5,883,493 relates to a battery pack including a plurality of cells and having an outer electronic memory electrochemical battery case. This electronic memory stores identification information of the battery and is capable of recording over time the maximum load capacity, the number of cycles, and other battery pack characteristics such as temperature. This information is then used to control the battery in the most efficient manner possible.

Patent application JP 2013-92398 discloses a method and a measurement system SOH electrochemical accumulator. The batteries are equipped with pressure sensors and voltage sensors. An external control circuit to the housing of the accumulator compares the pressure curves and tension the original curves recorded during the production of batteries, in order to determine the SOH of the cells.

JP 2012-243660 patent application describes an electrochemical cell equipped with an internal pressure sensor in the housing and a safety valve configured to open at a predetermined pressure to discharge if required internal overpressure housing the electrochemical cell. The pressure sensor indicates whether the valve has been opened or not and makes a decision as to the judgment whether or not the battery.

CN 201868536 U patent application relates to an electrochemical cell equipped with a pressure sensor and an electronically controlled solenoid valve, the solenoid valve being opened and closed as needed.

The known identification systems are arranged outside the electrochemical battery case. They can be copied separately and then attached to a non-compliant accumulator to the original battery safety specifications. There is thus a need to make them more secure identification systems.

In addition, the communicating systems RFID protocol may not be transmitting information over a very short distance. Identification systems for which communication is not performed by waves require the use of additional son. Each wire at risk of own failure, and so the use of multiple son for a battery results in an increased risk of failure proportional to the number of son.

Thus, there is another need to further improve electronic identification systems associated with batteries and their means of communication to make them more reliable.

The invention responds at least partially, to what (s) need (s).

Summary of the Invention

The invention provides, in a first aspect, an electrochemical accumulator comprising at least:

· An electrochemical cell consisting of at least an anode and a cathode from each side of an electrolyte,

• at least two current output terminals each connected to one or the other of the (of) anode (s) and (des) cathode (s),

• a first housing containing the (the) cell (s) electrochemical (s) sealed,

• a second housing attached to the interior of and / or integrated with the first housing defining therein a sealed confined volume,

• an electronic module arranged in said sealingly confined volume, the electronic module comprising at least:

- a memory,

a communication module adapted to receive and / or transmit data from and / or towards the outside of the first housing, a processor,

a processor adapted to receive and / or transmit at least data from and / or to the communication module,

the electronic module being electrically powered by (the) cell (s) electrochemical (s). The electronic module and the casing in which it is housed is an intelligent module. This function module can be attached to the inside of the storage housing during the manufacture of the latter, before closing and sealing the lid.

Thanks to the invention, an electrochemical cell becomes much more difficult to replace a battery of lower quality, in particular, does not comply with safety requirements. Indeed, the intelligence module which constitutes an identification system is housed completely inside the battery case.

The memory may be internal to the processor and / or included in the electronic module.

The module is powered by the electrochemical cell and does not require power from an external source. This ensures a complete autonomy of the electronic module vis-à-vis the outside.

According to a first embodiment, the first housing is metallic.

Metals of choice for the first housing can then be aluminum, steel, copper or alloys of these metals.

The first housing may alternatively be insulating, for example made of plastic.

The first housing may further include both conductive metal elements and insulating plastic elements.

Advantageously, the second housing may be metallic and attached to the first housing by soldering or welding by brazing or laser welding.

It is also conceivable to integrate the second housing to the first housing, i.e. to spare a cavity in one of the walls of the first housing, for example the lid of the first housing, and to close the cavity by a cap, thereby defining the second housing and a sealed confined volume.

In an advantageous embodiment, the accumulator comprises at least one current output terminal forming a sealed passage of the first housing.

In one embodiment, the electronic module is electrically connected to at least one output terminal of the electrochemical cell.

In a variant of this embodiment, the electronic module is connected to the current output terminal forming a sealed passage by a wire passing through sealing the second housing, the wire being electrically insulated from the second housing. According to a first alternative embodiment, the accumulator comprises a pressure sensor arranged inside the first housing, the pressure sensor being connected to the processor.

The pressure sensor may be a deformable system equipped with strain gauges, or a piezo -electric system.

According to a second alternative embodiment, the accumulator comprises at least one temperature sensor arranged inside the first housing, the temperature sensor being connected to the processor.

According to a third alternative embodiment, the electronic module comprises a current sensor and / or voltage suitable for measuring the current and / or voltage on the output terminals of the accumulator.

electrically connecting the electronic module to the first housing is used for supplying the electronic module directly into electrical energy through the electrochemical cell. For the same reasons, the electronic module may also be connected to a terminal forming bushing. These electrical connections can also advantageously be used by a current or voltage sensor to perform a measurement.

Thus, it uses the energy of the electrochemical cell for supplying all the components of the intelligent module.

The data collected by the various sensors can be registered as and in the memory and used to calculate different settings using the microprocessor or may be sent via the communications module to an external central unit so that the data are recorded and / or processed.

According to an advantageous variant, the electronic module comprises a balancing circuit adapted to modulate the output current of the electrochemical battery.

The role of the balancing circuit is to modulate output current to ensure proper operation of the electrochemical cell itself or to balance a pack battery.

According to a preferred embodiment, data is stored in memory prior to commissioning of the accumulator, the data being selected from an identifier of the accumulator and / or its position and / or a history of temperature and / or pressure and / or current and / or voltage. By "identifying" is meant a set of data used to identify the nature of the battery and / or for authentication of the battery securely. The identifier can thus contain a serial number and / or data detailing the type of electrochemistry of the electrochemical cell and / or identification data such as a security key or an anti-fraud program.

By "position" means the spatial position of the battery in a battery pack- comprising a plurality of accumulators. This allows an operator can know in particular where there is a defective accumulator or low effective capacity to replace it.

According to an advantageous embodiment, the communication module comprises an antenna adapted to receive and / or transmit data from the communication module and vice versa.

According to an advantageous embodiment, the first housing has a cover, the second housing being fixed to the cover of the first housing.

Advantageously, the electrochemical cell is a lithium battery.

The invention also relates, in its first aspect, to a method of communication between at least one accumulator and an electronic control unit, wherein each battery and control electronics exchange using the communication module described above for data selected from: the position of each battery and / or an identifier of each battery and / or the temperature and / or pressure within the first housing of each battery and / or the voltage on the output terminals of each accumulator and / or the current output of each accumulator and / or health and / or the state of charge of each battery and / or the history of health and / or state of charge and / or pressure within the first housing and / or temperature and / or output current and / or voltage to the current output terminals of each battery history being recorded in the memory.

According to a first embodiment, the control electronics uses the data exchanged in order to predict the effective capacity of each accumulator.

Advantageously, the electronic control can use the data to detect a malfunction of each accumulator. According to an advantageous variant, the data arriving at the electronic module are recorded in a history in the memory. This allows including considering adapting a battery pack to some use. For example, in the case of an electric car can be put in the pack battery of accumulators, more or less large effective capacity on the basis of duration and distance of the path to be performed.

There may also be replacing a given battery when it is no longer healthy. Knowledge of the position of the defective battery pack within the battery makes particular easy replacement to be performed for an operator.

The invention relates, in a second aspect to a method of communication between an electronic control and at least one electrochemical cell, the accumulator comprising at least:

• an electrochemical cell consisting of at least an anode and a cathode from each side of an electrolyte,

· A first housing containing the (the) cell (s) electrochemical (s) sealed,

• at least two current output terminals each connected to one or the other of the (of) anode (s) and (des) cathode (s),

• a second casing secured within the first housing defining therein a sealed confined volume,

• an electronic module arranged in said sealingly confined volume, the electronic module comprising at least:

a memory,

a communication module adapted to receive and / or transmit data from and / or towards the outside of the first housing, a processor,

a processor adapted to receive and / or transmit at least data from and / or to the communication module,

the method comprising a step of exchanging data between the control electronics and each battery by means of each communication module power line such that the output current of Γ (des) accumulator (s) electrochemical ( s) carries data encoded into an information signal. The invention thus takes advantage of the communication by power line (French acronym CPL) in order to exchange so both simplified and reliable data at a high speed directly on the carrier line of the current. Such a process is advantageous because it eliminates additional son for communication between an accumulator comprising sensors, that is to say, an accumulator which has data to be transmitted (e.g., sensor readings) and a control electronics. In other words, the control electronics is connected to the transmission line of the electric power which is also in this case the data transmission line. This avoids the use of a separate wire for data transmission. PLC communication is advantageous that the communication waves through an antenna such as RFID since its scope is greater. Finally, the absence of additional son simplifies battery-pack assembly of the SINCE no additional connection in addition to the connection of the current output terminals is required between different battery-pack batteries.

The control electronics is for example that of a secondary battery control system (in English, "Battery Management System", acronym BMS), or that of a pack battery having a plurality of electrochemical storage.

According to a first embodiment, a plurality of accumulators are connected in series, the control electronics being connected in shunt to the output terminals of each electrochemical cell. This embodiment is called fashion "local loop". By "local loop" is meant that each system consisting of a battery and the electronic control unit forms a loop. this local loop is termed because its size is reduced.

According to a second embodiment, a plurality of accumulators are connected in parallel, the control electronics being connected to the ends of the series. One calls this type of architecture "global loop" because more accumulators are connected in series with each other and that the control electronics is connected to the ends of the series of accumulators. In other words, the control electronics is connected to the input of the first accumulator and the output of the last accumulator connected in series. This loop contains at least three items, namely the electronic control unit and at least two accumulators. Advantageously, each storage processor can perform a scaling operation on the input information signal, regardless of the existing modulation upstream. By "equally" means that the processor of each accumulator does not perform scaling operation following a prior reading of the signal from its input.

Alternatively, each storage processor may perform on the powerline a modulation operation on the input information signal at a proper time interval to each accumulator.

In other words, each processor is adapted to perform time multiplexing.

According to an advantageous embodiment, each connected downstream electrochemical cell of another battery is reading information on the powerline, and plotting on the powerline in addition to the information signal the upstream information signals.

Advantageously, the information signal can carry data selected from: the position of each battery and / or an identifier of each battery and / or the temperature and / or pressure within the first housing of each battery and / or the voltage the current output terminals of each battery and / or the output current of each battery and / or health and / or the status of each battery charge and / or the history of health and / or state of charge and / or pressure within the first housing and / or temperature and / or output current and / or voltage on the output terminals.

detailed description

Other advantages and features of the invention appear better on reading the detailed description of examples of implementation of the invention provided for illustration and not limitation with reference to the following figures among which:

Figure 1 is a sectional view of an accumulator according to the invention,

- Figure 2 is a close-up sectional view of a battery lid according to the invention,

- Figure 3 a close-up perspective view of the cover according to a variant of the invention, - Figure 4 is a sectional perspective view showing the interior of the intelligent module of the invention,

- Figure 5 is a block diagram of the accumulator according to the invention,

- Figures 6A and 6B show the form of the correspondence between state of charge and state of tension for electrochemical cells of different kinds,

- Figure 6C shows in the form of curves as a function of the state of charge pressure for cells which have undergone a different number of cycles,

- Figure 7 is a block diagram for determining the SOC according to the invention,

- Figure 8 shows the pressure distribution for a population of cells and a method for selecting reliable cells,

- Figure 9 shows the evolution of the effective capacity of a battery based on the internal pressure to the first housing during the life of the accumulator,

- Figure 10 shows in curve form the SOH based on the internal pressure in the first housing,

- Figure 11 shows a modulation operation performed by PLC,

- Figures 12 and 13 show the operation diagram of an internal module according to the invention by waves or by LC,

- Figures 14A and 14B illustrate the operation of a battery pack-local loop or global loop in accordance with the invention,

- Figures 15A and 15B illustrate the signal transmission according to whether or not reading and carry signal by successive accumulators connected in series.

1 shows an electrochemical cell 1 according to an embodiment of the invention. This electrochemical cell 1 includes a housing 6 and two current output terminals 2 and 4. Within the housing 6 is arranged in a sealed manner an electrochemical cell C. A second housing 7 is arranged inside the housing 61. the interior of the housing 7 defines a sealed confined volume 70.

Figures 2, 3 and 4 further illustrate the accumulator 1 and particularly the second housing 7. In this embodiment, the housing 6 is made of metal, for example aluminum alloy, and the C cell is an electrochemical cell lithium. We can see in Figure 2 that the first housing 6 of the battery is sealed by a cover 61. A first current output terminal 2 is fixed to the lid 2 by means of a laser weld 21. The cover is connected to the positive electrode of the electrochemical cell C. Thus, the current output terminal 2 is the positive pole of the electrochemical cell 1.

The second current output terminal 4 is a terminal through the cover 61.

A gasket 41 electrically insulates the current output terminal 4 of the metal cap 61 through which it passes. The second current output terminal 4 is connected to the negative electrode of the electrochemical cell C. The current output terminal 4 thus constitutes the negative pole of the electrochemical cell 1.

The second housing 7 houses in its sealingly confined volume 70 an electronic module 72. In this embodiment, the second housing 7 is made of metal and welded to the cover 6. Other fixing methods are conceivable, such as gluing, riveting, clipping, overmolding or other suitable technique for securing the second housing to the first. In this case, the first and second housing are both of metal, but they can also be in other materials, for examples plastic. The binding mode can be adapted according to the material.

Welding the second metal housing 7 to the metal cover 61 allows the electrical connection between the positive electrode of the electrochemical cell C and the second housing 7. The electronic module 72 is then connected by means not shown to the second housing 7 wire . the electronics module 72 is thus electrically connected to the positive electrode of the electrochemical cell C.

A wire 71 connects to the same lower part of the power output terminal 4, that is to say the part of the current output terminal 4 located inside the housing 6, the electronic module 72. the electronics module is thus electrically connected to the negative electrode of the electrochemical cell C. It should also be noted that the wire 71 is electrically insulated from the housing 70 and the wire 71 passes through the housing 70 in a sealed manner.

The electronic module 72 is powered by the electrochemical cell C with its connections to the positive electrode and the negative electrode of the electrochemical cell C.

According to the embodiment of the invention shown in Figure 4, the housing 7 includes a hollow extension 75 leading to the interior of the electrochemical housing 6 through a gas return port and / or liquid 76. The hollow extension 75 comprises a pressure sensor (not shown) connected to the processor of the electronic module 72. Alternatively, it is also possible to have a pressure sensor outside the second housing 7 connected to the processor of the electronic module 72 by a wire.

In the embodiment shown in Figure 4, a temperature sensor is arranged within the tight confined volume 70 and is connected to the processor of the electronic module 72. Alternatively, the temperature sensor (not shown) may be disposed in the outside of the second housing 7 and connected to the processor of the electronic module 72 by a wire.

There is shown in Figure 5, the operation of an electrochemical cell of the invention. The electronic module 72 is connected to both electrodes of the electrochemical cell C through a voltage regulator. The electronic module 72 has a current sensor and a cell voltage sensor C, these being connected to the processor. Specifically, the current sensor is connected to the processor of the electronic module 72 which is itself powered by the cell.

The processor of the electronic module 72 receives data from temperature sensors, pressure, current and / or voltage and optionally one or more strain sensors (strain gauge) bonded (s) of the housing wall 6 accumulator. The processor can also save and read data in a memory. The measurements of the various sensors can be recorded and retained in time, thus creating a temperature history, pressure, current and voltage. Other values ​​may also be stored after being calculated, for example by the processor, such as SOC, SOH or the safe state.

The processor is also connected to a communication module and exchanges data therewith. The communication module may include an antenna and communicating by waves. The communication module may also be connected to the current output terminals and communicate CPL.

As shown in Figure 5, the communication module can communicate with a neighbor or with a battery electronic control of a battery-pack.

The memory can contain an identification number of the cell and if appropriate, its spatial position in a pack battery. It may also contain a security key or an anti-fraud security program in order to authenticate the battery and thus guard against the use of non-compliant batteries.

Finally, the electronic module comprises a balancing circuit which is adapted to have a balancing effect on the electrochemical cell C. This circuit comprises for example a resistance allowing the cell to discharge by flowing a weak current in the resistor . The processor may transmit instructions from the control electronics to the balancing circuit. The balancing circuit is thus controlled by the control electronics.

Data analysis

The electronic module has data that are:

"fixed" data recorded in the memory (eg identifier, security key, position, safety program, type electrochemistry) of "instant" data from the various sensors (temperature, pressure, current, voltage), data historical from these sensors stored in the memory, the data communicated by the communication module, and historical data provided by the communication module module stored in the memory.

These data are not necessarily all present in the memory, it is possible to use only certain data according electrochemistry of the electrochemical cell or according to the sensors which has the accumulator.

Other data may also be calculated from the instantaneous data, historical or reported data. These data can be the SOC, the SOH, the security status or the power supplied by the cell, the number of cycles that the cell has performed or the age of the electrochemical battery.

Some of the data stored in memory may be measured by the sensors during manufacture of the accumulator, for example during the first cycling of the battery (cycle comprising a charging and discharging).

Among the important data include, for example: the instantaneous temperature, available through the temperature sensor, the maximum and minimum temperatures of temperature history, the instantaneous pressure available through the pressure sensor in the module, the maximum pressure and minimum pressure history, the energy supplied by the cell over a defined period (a predetermined period or since the start of the life of the cell, for example), the voltage and the instantaneous current of the cell.

Measured data can for instance achieve the control electronics of a storage battery control system (in English, "Battery Management System" acronym BMS), which incorporates a safety device. This is notably to cut the power if abnormal values.

Knowledge of the temperature of the electrochemical cell by means of a temperature sensor is a key element for use in the electrochemical cell. the temperature can be used for example to predict the lifetime of the battery, limit its use in case of situations in inadequate temperature ranges (eg limitation of the load in case of low temperature or shutdown beyond a certain temperature) or guard potential detected by a temperature sensor malfunction (eg, degradation of an electrochemical cell cross-link causing overheating in the event of high current pass).

Another very important factor is the pressure. Knowledge of the internal pressure in the first housing 6 is source of information.

By knowing the internal pressure in the housing 6 or instantaneously or based on a history of pressure and the instantaneous value, it is possible to have access to valuable information.

The internal pressure can for example be used as alarm operation. Beyond a certain value of internal pressure, this means that the cell returns in later life. This can also be information indicating a faster than normal degassing. For example, in the case of early micro short circuit, electrochemical cells can produce a larger gassing in normal use.

Thus, by monitoring the pressure value or its evolution over time, it is possible to prevent causing a short circuit to a thermal runaway, for example. The pressure can therefore indicate the SOH, but also the security status through different approaches. Other determining the SOH or the security status of approaches are also possible. When manufacturing electrochemical accumulators, the steps of forming the electrochemical cell and the first cycling generate a volume of gas which depends on many factors. From the internal pressure of the housing, it is possible to identify certain batteries as defective or less viable. Indeed, a gas evolution exceeds a predetermined value may indicate for example a composition of non-compliant electrolyte with a higher water content than a predetermined value, or that too electrolyte was poured.

In all cases, the use of a battery containing an electrochemical cell having a defect in a battery pack is not recommended. This electrochemical cell present probably much lower performance than expected, with a short life, or self discharge for example. This drop in performance directly affects the entire pack-battery.

Pressure may also be an indicator of future performance of a cell and can be used in a product production cycle to discriminate the least efficient products.

The internal pressure of an electrochemical battery may sometimes vary depending on the SOC. Knowing the pressure, it is possible to estimate the SOC with a clean profile each electrochemistry. The pressure can be a SOC indicator.

The various aspects of monitoring battery condition (state of charge, state of health and safety and reliability at the factory) are detailed below.

Determining the state of charge

The SOC of a battery is a leading data in the management of its use. It indicates the amount of power available and therefore the autonomy eg for electrical equipment such as vehicles, telephones or backup systems. ATR is a given that the user wants to know at any time. In the case of a vehicle for example, it allows him to know the distance he can still go, and possibly adjust its travel strategy and / or charging. Poor knowledge of the SOC has important implications for the use of the available energy strategy. Also in the case of a vehicle, if the autonomy announced less than the real autonomy, the risk of missing energy to perform the end of the planned route was found. For a number of electrochemical electrode pairs, the voltage curve in open circuit makes it easy to know the percentage of available capacity because it is bijective. A specific cell voltage corresponds a single charge state. This is the case of electrochemical cells based on NCA / Graphite (CAS: Aluminum Nickel Cobalt) whose load curve as a function of voltage is shown in Figure 6 A.

For other electrodes electrochemistries, it is impossible to know the charging status by reading only the tension. This is the case for example of the electrochemical couple LFP / LTO (LFP: acronym for Lithium Iron Phosphate and LTO: acronym for Lithium Titanate) which depending on the voltage charge curve is shown in Figure 6B. There is an important step in preventing this curve for a given voltage to know the SOC.

In this case, it is easier to use the pressure as an indicator of SOC.

A set of pressure measurements is necessary to establish a base reference curve used in determining the SOC (a measured pressure corresponds to a state of charge). Since most electrochemistries generate gas non-reversibly at progressively successive charging and discharging cycles, it is not possible to establish a single fixed reference curve. In addition, some may have electrochemistries representing the pressure curves depending on the load condition which are not bijective (a pressure information can contain two charge states).

Therefore, simply complete the instantaneous pressure by a history of pressure in order to adjust the reference curves indicating the state of charge based on the pressure as shown in Figure 6C.

In order to choose the correct pressure / SOC, the strategy to be employed is to measure the pressure when the accumulator is charged to a value showing a specific feature to clearly identify the state of charge. In most cases, it is possible to use an alternative means to the pressure for detecting a state loaded or 100% 0% loaded. For example, for voltage curves according to the load condition that a profile integrating a large tray (as in Figure 6B), most of the time, two SOC ends have a different tension of the tray (see Figure 2). We can use the voltage detection as the nearby beaches of 100% or 0% load. At this particular point of SOC, the pressure is measured. It has then choose in historical a curve of the SOC as a function of the pressure corresponding to our cell state (indexed particularly on aging, see Figure 6C).

Note that it is possible that this choice is also to modulate depending on the system temperature. Indeed, the pressure of the cells can vary depending on the geometry, materials used and electrochemistry of the battery in question, even if the state of charge does not change. This is due to differential thermal expansions of the materials used to manufacture such a cell. A temperature measurement is thus advantageous because it strengthens the measurement accuracy of the SOC.

It should be noted that for Li-ion batteries, the electrodes of the materials expand or contract as they have received or released lithium ions. In other words, the materials expand depending on the SOC. The volume expansion coefficient γ is defined as the volume of the mesh lithiated divided by the volume of the délithiée mesh.

The following tables give the values ​​of the volume expansion coefficients for different materials and different types of cells.

Figure imgf000021_0001

Figure imgf000021_0002

In the case of LFP-G cell with a capacity of 17 Ah, a variation of 0.1 bar can be measured, despite the low volume expansion A. It follows that the method is applicable to other accumulators Li- ion. The flowchart of the SOC estimation process is shown in Figure 7. database is meant a set of historical different data.

For the creation of the database, two methods are proposed.

The first method requires an adequate characterization of the electrochemical cell prior to using the method described in this document. It is then necessary at the time of development of the cell perform at different temperatures pressure recordings, different health conditions, and different states of charge in order to create the database. With all this data, an integrated base is then constituted in the electronic module of the electrochemical cell and used early in the life of new cells as described above.

The second method is based on self-learning. Indeed, it is not necessary to provide an initial characterization in different configurations. Using recordings made on each cell As his life and made up little by little the database.

The disadvantage of the second method is that in the early parts of the life of the cell, the accuracy of the SOC is less than with the first method. By cons, as and extent of the life of the cell, the base reinforcing the accuracy of the SOC grows.

A final solution is to combine both methods to combine the advantages: a useful basis from the beginning of the life of the cell, and completed as and when the life of the electrochemical cell. The base becomes increasingly precise.

Thus, when choosing the profile, thus can either assume that the database is fairly comprehensive and directly read pressure and temperature to estimate the SOC, or redo a charge and discharge cycle in conditions of temperature data to specify the database, or both.

Determining the health status

The study of aging mechanisms of a battery is very complex, since the causes of aging are many. aging mechanisms occur either during the use of the accumulator stages (cycling in aging) or during the resting phases (calendar aging). Knowledge of the health of an electrochemical cell is important because it reflects both its ability to meet the application and intrinsic safety. The state of health is so closely linked to the security state.

An electrochemical battery in poor health will not be able to store or deliver the expected energy and could be potentially dangerous in cases of failure.

The consequences of aging are often analyzed in the literature to introduce measures systems that allow terms to give the health status of an electrochemical battery. These measurements are typically the measurement of the resistance of the Li-ion cell by impedance spectroscopy or draws current during cycling, the measurement of the voltage of the cell, or measuring the cell capacity.

One can also measure the deformation of packaging or consecutive rigid housings to an internal volume expansion.

The data measured during the aging premature of a lithium battery (high resistance, high voltage or low capacity) result with a delay time the passivation of the electrodes on the surface, bad diffusion of the lithium ions in the electrodes due to too low porosity of the electrodes, degradation of the electrolyte (the presence of water or high voltage), a loss of tightness of the housing, of bad welds, gradient separator, or debonding of the electrodes.

In the case of a pack battery, the BMS and incorporates a safety device which cuts off the current in case of abnormal values ​​recorded. Inevitably, more detection of faulty battery occurs, the sooner it can be quickly removed from the production circuit.

Unfortunately, the electrical measurements outlined above are mainly carried out during the life of the electrochemical cell when it is already assembled pack battery and late detection of abnormal values ​​causes an immediate stop of the module to prevent thermal runaway leading to explosions.

The electronic module according to the invention allows the measurement of the pressure inside the first housing and thereby provides a method for determining the health status of an accumulator upstream of the usually used. This method will enable to understand the internal degradation for example by allowing a preliminary release of the gas or to remove the faulty storage cell further upstream.

As already indicated, an internal pressure sensor can be integrated with the electronic module of the battery. For a given state of charge, the internal pressure increases monotonically during aging, so that it is possible to predict the remaining life of the battery from its pressure measurement. Indeed aging generates parasitic reactions within the element forming gas and increases its pressure. At each cycle the electrodes also undergo expansion / contraction volume generating an increase / decrease in cyclic pressure. This mechanical effect is not completely reversible, so that the free volume is reduced during aging in the interior of the cell and its pressure increases, especially in the case of electrochemical lithium batteries.

There is also a pressure limit is not exceeded to maintain the integrity of the casing, which can define a criterion for end of life of an electrochemical battery.

It is also conceivable degassing to release accumulated pressure and prolong the life of the element. For example, it may act during manufacture with a removable stopper which will subsequently be replaced by the definitive closing rivet, or during periodic maintenance if addition of a valve on the element.

There is shown in Figure 9 the monotonous increase in pressure due to irreversible effects and decreased capacity for a cylindrical electrochemical battery of electrochemical couple LiFeP04-graphite 16Ah. discharges charge cycles is subjected to the accumulator at a 1C scheme (I = 16A). It is possible to connect the capacity or resistance level of internal pressure, which evaluates health status.

It is also desirable to more accurately placing themselves in a state of charge and temperature known to improve the accuracy of determining health status.

Indeed, the internal pressure varies little with temperature (in the following first approximation the ideal gas law, pressure variation of 0.3% / ° C in the example). for example one can easily add a thermocouple to an electrochemical accumulator or a set of electrochemical accumulators. The pressure measurement can be made static (not in use), the room temperature for a complete battery pack may be sufficient in some cases to know the temperature of each battery. In some other cases, if the ambient temperature measurement is insufficient to characterize the local temperature, then it sends a local measurement in each accumulator.

On the other hand the pressure varies with the load condition, as can be seen in Figure 6C. Move to a state fixed charge increases accuracy on health.

If we define the condition S of the cell initial capacity and capacity Qini Q according to the following formula: S = 100 (2xQ / Qini -1), we obtain the graph in Figure 10.

The conditions for the chart of Figure 10 have been chosen such that the internal pressure is that 50% of the SOC and the temperature is 25 ° C.

Determination of the reliability of a cell

So far, for more reliable battery production, a number of specific cell parameters were controlled training output to be of quality.

One can identify at first a few individual criteria (specific to each cell) such as cell capacity (load and or discharge), the internal resistance of the electrochemical cell (usually resistance measured with a current peak or high frequency resistance measured) self-discharge (loss of capacity over time), or the dimensions and the aspect of electrochemical accumulator.

Electrochemical batteries are also evaluated by deduction. A number of electrochemical batteries are taken from batches and tested to check various criteria (this assessment being destructive, it can not be done on 100% of products) such as the lifetime (in one or more temperatures ) according to one or more plans charge / discharge behavior or abusive testing (short-circuit, overload)

To further increase the reliability of electrochemical lithium batteries, can use a clean behavior for any lithium-ion cell that initially appears during power training: degassing. Indeed, when the electric formation (the first charge and discharge cycles), the electrodes react with the electrolyte and the charged current plans, and generates gas. This phenomenon also occurs in lithium polymer batteries.

Following this statistically gas formation, it is possible to detect during the production of the electrochemical storage anarchic behavior that reveal risks for the use of some of them in products.

This process makes it possible to distinguish between viable storage of those who are not.

The present invention allows the determination of cell viability during the production phase located between the electrolyte filling and made available for use or set-battery pack

The internal pressure in the accumulator is the central information used in the invention. This makes it possible to sort between viable batteries and others.

The determination method is based on the knowledge of this pressure.

To evaluate each battery individually, more specifically it uses the gas pressure after the electric forming, that is to say, after it is made the electrochemical cell. This may be the pressure just after the forming step, but much later, after a step of such prolonged storage (this step is often used to check the batteries self-discharge).

The individual pressure of each battery must be between a maximum and a minimum specified.

Both limits are established on the basis of a deemed healthy population of cells. then forming a statistical representation of the pressure at time t. This population gives us the maximum and minimum acceptable pressure following a rule set. A first example rule can be the transfer of existing limits limits for production. So :

- the minimum internal pressure of the healthy population is the minimum acceptable, and

- the maximum internal pressure of the healthy population is the maximum acceptable.

It may also decide to rule on a statistically - average pressure of the healthy population + 3 sigma is the maximum acceptable, and

- the average of the pressure of the healthy population - 3 sigma is the minimum acceptable, sigma being the standard deviation of the pressure of the healthy population.

This method is shown in Figure 8.

To be declared viable, each test battery must have its pressure between the acceptable minimum and maximum acceptable, because too low or too high internal pressure is a sign that the battery is defective.

The cause of internal pressure of the battery can be at least:

- leakage: in this case, the electrolyte of the electrochemical cell will be gradually contaminated and holding in the electrochemical cell aging will not be good,

- a filling defect: the amount of electrolyte is inserted too low. This may impact the service life, but also the behavior of the cell safety if the dead volume is important in case of abusive situation (the dead volume is a volume of the cell left voluntarily without electrolyte)

- a defect or lack of a component within the cell or defect on the electrodes (porosity, thickness ...).

A maximum pressure above may be related to:

- a filling defect: the amount of electrolyte inserted is too great. The dead volume of the cell is diminished and adverse consequences may occur in the event of abusive situation,

- pollution of the electrolyte or the electrodes: pollutants (such as water for example) are found in large quantities in the cell, generating more gas in the formation. This is a good indication that the cell performance over the long term will not be good, for example, that the life will be shortened or

- failure on the electrodes (porosity, thickness ...).

Note that this method can be used with a sensor adapted to measure the pressure inside the first casing that is arranged inside or outside of the first housing. Data communication by CPL

The principle of data transmission CPL is illustrated in FIG 11. It is superimposed on the voltage of a cell, a signal of higher frequency and of low energy. This signal propagates along the power line and can be received and decoded at a distance.

Thus, instead of communicating the data wave as shown in Figure

13, an accumulator provided with an electronic module may, according to the method of the invention, communicating data directly to the output current of the battery.

This process is advantageously carried out in the data communication frame of a battery to an electronic control. The control electronics is indeed connected to the current output terminals of a storage battery, either directly or indirectly. The PLC communication has advantage of being able to be either directly to control electronics, or through one or more accumulators connected in series. These two embodiments, respectively called "local loop" and "global loop" are illustrated in Figures 14A and 14B.

The control electronics and reads the voltage U either individually across each battery, or collectively across a series of accumulators.

If the electronic control unit reads the voltage individually to the current output terminals of each storage cell (user local loop) it is not necessary to adjust each electronic module of each storage cell for reading a signal CPL. The simple issue enough.

Depending on the mode in global loop, beyond a certain number of serial accumulator, it may become necessary to take into account the frequency attenuation due to the crossing by the signal of an accumulator. Each successive accumulator acts as a filter having a characteristic and this results in an attenuation of the original signal (see FIG 15A).

Thus, it may be advantageous that each electrochemical cell and réémette read data received from the previous accumulator, by superimposing its own modulation operation. This operation can be done by time division multiplexing (data transmission in different time slots to each cell) or not. Modulation of signal CPL can be done according to any method of modulation CPL known to those skilled in the art (amplitude modulation and frequency). Communication by PLC advantageously eliminates the additional son connection connecting the control electronics to the different sensors of each accumulator.

Other variations and improvements of the invention just described can be envisaged without departing from the scope of the invention.

Claims

1. An electrochemical battery (1) comprising at least:
• an electrochemical cell (C) consisting of at least one anode and a part of cathode side of an electrolyte,
• a first housing (6) containing the (the) cell (s) electrochemical (s) sealed,
• at least two current output terminals (2, 4) each connected to one or the other of the (of) anode (s) and (des) cathode (s),
• a second housing (7) fixed inside the first housing defining therein a sealed confined volume (70),
• an electronic module (72) arranged in said sealed confined volume (70), the electronic module (72) comprising at least:
a memory,
a communication module adapted to receive and / or transmit data from and / or towards the outside of the first housing, a processor,
a processor adapted to receive and / or transmit at least data from and / or to the communication module,
the electronic module being electrically powered by (the) cell (s) electrochemical (s).
2. Electrochemical battery according to claim 1, the first housing being metal.
3. Electrochemical battery according to claim 2, the second housing being made of metal and fixed to the first housing by soldering or laser welding.
4. Electrochemical battery according to any preceding claim, the battery comprising at least a current output terminal forming a sealed passage of the first housing.
5. A battery according to one of the preceding claims, the electronic module being electrically connected to at least one output terminal of the electrochemical cell.
6. Electrochemical battery according to claim 5 in combination with claim 4, the electronic module (72) being connected to the current output terminal forming a sealed pierced by a thread (71) passing sealingly the second housing (7) , the wire being electrically insulated from the second housing.
7. Electrochemical battery according to one of the preceding claims, comprising a pressure sensor arranged inside the first housing (6), the pressure sensor being connected to the processor.
8. Electrochemical battery according to one of the preceding claims, the electronic module comprising a current sensor and / or voltage suitable for measuring the current and / or voltage on the output terminals of the accumulator.
9. Electrochemical battery according to one of the preceding claims, the electronic module comprising a balancing circuit adapted to modulate the output current of the electrochemical battery.
10. Electrochemical battery according to any preceding claim, wherein data is stored in memory prior to commissioning of the accumulator, the data being selected from an identifier of the accumulator and / or its position and / or a history of temperature and / or pressure and / or current and / or voltage.
11. Electrochemical battery according to one of the preceding claims, wherein the communication module including an antenna adapted to receive and / or transmit data from the communication module and vice versa.
12. Electrochemical battery according to one of the preceding claims, the first housing having a cover (61), the second housing being fixed to the cover (61) of the first housing.
13. Electrochemical lithium secondary battery according to one of the preceding claims.
14. A method of communicating between at least one accumulator according to one of the preceding claims and an electronic control unit, wherein each battery and control electronics exchange by means of the data communication module selected from: the position of each accumulator and / or an identifier of each battery and / or the temperature and / or pressure within the first housing of each battery and / or the voltage on the output terminals of each battery and / or the output current of each battery and / or the health and / or the state of each battery charge and / or the history of health status and / or state of charge and / or pressure within the first housing and / or temperature and / or output current and / or voltage on the output terminals, the history of each cell being stored in the memory.
15. A communication method according to the preceding claim, the control electronics using the exchanged data, to provide the effective capacity of each accumulator and adapt its charging current and discharge current.
16. A communication method according to claim 14 or 15, the control electronics using the data, to detect a possible malfunction of each accumulator and adapt its charging current and discharge current.
17. A method of operation of the accumulator according to one of claims 1 to 13, the data arriving at the electronic module being recorded in a history in the memory.
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