• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
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  • 优先权
    • 专利摘要:
    The present invention relates to a method for decreasing the internal impedance of a lithium battery chosen from Lithium-Metal-Polymer batteries and Lithium-ion polymer batteries, said method comprising at least a first step of carrying said battery at a temperature T1 of at least 50 ° C, and at least a second step during which said battery is maintained at the temperature T1 while applying a pressure of at least 0.5 bars.
    公开号:FR3052599A1
    申请号:FR1655239
    申请日:2016-06-08
    公开日:2017-12-15
    发明作者:Margaud Lecuyer；Vincent Bodenez；Philippe Bernardo；Mathieu Dru；Marc Deschamps
    申请人:Blue Solutions SA；
    IPC主号:
    专利说明:

    The present invention relates to the field of lithium batteries, in particular Lithium-Metal-Polymer (LMP) batteries and lithium-ion polymer (Li-Po) batteries.
    More specifically, the invention relates to a method of heat treatment of a lithium battery to optimize performance, both at the beginning of battery life and longer term.
    Lithium batteries are particularly intended for motor vehicles as well as stationary storage of electrical energy.
    LMP batteries are generally in the form of an assembly of superposed thin films (winding or stacking of the following pattern (electrolyte / cathode / collector / cathode / electrolyte / anode) on n turns) or n thin films stacked (cut and superimposed , ie n stacks of the aforementioned pattern). This unitary unit stacked / complexed has a thickness of the order of a hundred micrometers. Four functional sheets come into its composition: i) a negative electrode (anode) ensuring the supply of lithium ions during the discharge of the battery, ii) a solid polymer electrolyte conductive lithium ions, iii) a positive electrode (cathode) composed an active electrode material acting as a receptacle where the lithium ions are interposed, and finally iv) a current collector in contact with the positive electrode and to ensure the electrical connection. The negative electrode of the LMP batteries is generally made of a sheet of lithium metal or a lithium alloy; the solid polymer electrolyte is generally composed of a polymer based on poly (ethylene oxide) (POE) and at least one lithium salt; the positive electrode is usually a material whose working potential is less than 4V vs Li + / Li (ie the insertion / deinsertion potential of lithium is less than 4V) such as for example a metal oxide (such as for example V2O5 , LiVaOs, LiCoO2, LiNiO2, LiMn204 and LiNiO.5Mno.5O2 ...) or a UMPO4 type phosphate, where M represents a metal cation selected from the group Fe, Mn, Co, Ni and Ti, or combinations thereof. cations, such as LiFePO4, and also contains carbon and a polymer; and the current collector is generally made of a sheet of metal. The conductivity of the ions is ensured by the dissolution of the lithium salt in the polymer used in the composition of the solid electrolyte.
    Li-Po batteries generally consist of a positive electrode of the same type as that of LMP batteries, a gelled polymer electrolyte comprising a polymer and a lithium salt dissolved in a solvent, and a negative electrode in one. carbonaceous material such as graphite.
    Lithium batteries, and particularly LMP batteries, have a number of advantages.
    First, the mass density of LMP batteries is in the range of 120 to 180 Wh / kg, which is at least 2.5 times higher energy density than thermal car lead-acid batteries (30-50 Wh / kg). The LMP batteries also have no memory effect and it is therefore useless to unload them completely before recharging, as in the case of some other technologies (Ni-Cd). Finally, with a voltage identical to that of lithium-ion batteries (of the order of 3.4 V), LMP batteries are maintenance-free and have a life of almost 10 years, which is interesting. from a commercial point of view and makes them relevant for applications requiring electric pulls.
    However, LMP batteries also have certain disadvantages. Indeed, to use, they must be maintained at a temperature of about 60-80 ° C, which almost forces them to maintain charging leaving the vehicle connected to the sector when it does not roll. Otherwise, the LMP batteries are emptied in a few days by maintaining their temperature.
    The internal resistance of lithium batteries, in particular LMP batteries, also called internal impedance, causes a voltage drop in discharge and induces a limitation of performance in terms of power or self-heating. The internal resistance of a battery is defined as the opposition to the flow of current in a battery. There are two essential components for this resistance: electronic resistance and ionic resistance. Their combined effect is called total effective resistance. The electronic resistance includes the resistivity of the materials used such as the cover metal and the internal components but also the parasitic resistances related to the different connectors making up the battery. Ionic resistance is the opposition to the passage of current in the battery due to various factors such as the ionic conductivity of the electrolyte and the electrodes as well as the quality of the interfaces.
    The internal resistance is generally low at the beginning of the battery life but tends to increase during the life of the battery, which has the effect of gradually reducing its performance as the numerous charging cycles and until it reaches a value that is too high to allow it to continue to be used for the purposes for which it was originally designed. In general, the higher the initial internal resistance of a battery, the more limited its performance will be.
    The initial internal resistance of a battery can be minimized by choosing the raw materials used in the composition of the electrodes as well as by improving the quality of the assembly.
    For example, it has already been proposed, in particular in the patent application US 2014/0197799, a method for decreasing the initial internal resistance of an LMP battery consisting of over-discharging said battery, that is to say discharging the battery beyond 100% of its nominal capacity, and for a time sufficient to reduce its internal resistance. More specifically, the method consists of over-discharging the LMP battery until it reaches a voltage of between 0.5V and 2.0V (second plateau), then recharging said battery to its maximum capacity at a voltage of 3.6V. It is indicated that this process makes it possible to reduce the internal resistance of an LMP battery by approximately 40%. However, this method is not entirely satisfactory insofar as the decrease of the internal resistance is not necessarily homogeneous. This method can indeed lead to differences in resistivity between different areas of the battery, the over-discharge applied by this treatment is not necessarily passed on with the same intensity in all the elements constituting the battery. Thus, this method is really effective only for batteries in which the active material is isotropically connected within the electrode at the time when the overdischarge is performed.
    There is therefore a need for a method making it possible to overcome the disadvantages of the processes of the prior art, and in particular for a process making it possible to significantly and sustainably reduce the internal resistance (internal impedance) of lithium batteries, in particular LMP batteries. and Li-Po, both at the beginning of life and in the long term, this method being applicable to any type of LMP or Li-Po batteries, and in particular to LMP and Li-Po batteries in which the nature of the active ingredient d Positive electrode is not limited, particularly to batteries in which the connection of the positive electrode active material is anisotropic.
    This object is achieved by the method which is the subject of the present invention and which will be described below.
    The subject of the present invention is therefore a method for heat treatment of a lithium battery chosen from Lithium-Metal-Polymer batteries and lithium-ion polymer batteries, said battery comprising at least one positive electrode, at least one polymer electrolyte and at least one negative electrode, said method being characterized in that it comprises: 1) at least a first step of bringing said battery to a temperature T1 of at least 50 ° C, 2) at least a second step during said battery is maintained at the temperature T1 while applying a pressure of at least 0.5 bar, said steps 1) and 2) being performed before the first charge of said battery.
    The method according to the present invention makes it possible to improve the performance of the LMP and Li-Po batteries. It is particularly suitable for LMP batteries, and leads in particular: - to a decrease in the internal resistance of the LMP battery, - to an improvement in its performance in power, - to an increase in energy, - to a lowering of the activation phenomena at the beginning of life, - at an improved lifetime.
    According to the invention, the term "significantly reduce the internal resistance" means a decrease in the internal resistance of the battery at the end of step 2) by at least 2% relative to the internal resistance. initial, that is to say the internal resistance of the battery measured before the start of step 1) of the method according to the invention.
    These advantages result from the effects of the heat treatment of the process according to the invention, which notably generates an optimization of the interfaces between the different layers of the battery and consequently a uniformization of the connection properties of the grains of active material and a homogenization of the resistivity between different areas of the battery.
    The temperature T1 preferably varies from 50 to 120 ° C., and even more preferably from 70 to 105 ° C.
    The battery can be brought to the desired temperature T1 for example by means of its own heating elements or by hot storage.
    During step 2), the pressure applied to the battery preferably varies from about 0.5 to 10 bar, and even more preferably from 1 to about 7 bar.
    The desired pressure can for example be applied to the battery using springs. Step 2) is conducted for a time sufficient to significantly decrease the internal resistance of the LMP battery.
    According to the invention, the duration of step 2) generally varies from about 5 hours to 1 week, preferably from 5 to about 72 hours, and still more preferably from 5 to about 25 hours.
    The internal resistance of the battery before and after application of the method according to the invention can be measured by applying to the battery terminals, an AC voltage of known frequency and amplitude and by measuring the voltage and the resulting AC current. The internal resistance or internal impedance (Ri) can for example be calculated using Ohm's law according to equation (1) below:
    (1) in which: - AU is the variation of the potential between the state of rest and the state under current and - ΔΙ is the variation of the current imposed at the beginning of discharge.
    Thus, the measurements and internal resistance values referred to in the present application were determined according to the method indicated below, under the following conditions: the battery is subjected to a charging current of 8A for 30 sec then left to rest. The difference in voltage under current with respect to the voltage measured at rest thus makes it possible, via Ohm's law, to calculate the internal resistance value.
    These measurements do not affect the performance of the battery. They can be performed while the battery is in use or can be used to continuously monitor the evolution of the internal resistance, and therefore the performance of the battery during different charging / discharging cycles. Step 2) of the method according to the invention can indifferently be conducted while leaving the battery voltage fluctuating, or by imposing a determined value of voltage on said battery.
    When step 2) is performed under voltage, the battery may for example be placed in potentiostatic hold at a voltage corresponding to the initial state of charge of said battery after assembly, plus or minus 10%, and preferably, more or less 2%.
    According to the invention, the term "discharged battery" means a battery which is discharged at more than 90% of its nominal capacity, and preferably at more than 98%. At the end of step 2), the battery can be used in a nominal way.
    According to a particular embodiment of the invention, and only when the lithium battery is an LMP battery, it is recommended to follow steps 1) and 2) of the method by an additional step of overcharging the battery.
    Thus, according to this embodiment, the method according to the invention is applied to an LMP battery and further comprises a step 3) of overdischarge of said LMP battery.
    Although not mandatory, this additional over-discharge step makes it possible to further accentuate the decrease in the internal resistance of the LMP battery obtained after steps 1) and 2) of the method according to the invention.
    When performed, step 3) of over-discharging the LMP battery is preferably conducted until the battery is discharged beyond 100% of its rated capacity, particularly until the battery is over-discharged from 2 to 40% of its nominal capacity, and even more preferably from 8 to 20% of its nominal capacity. The overdischarge step 3) may, for example, be carried out by applying to the battery an overdischarge current at an intensity corresponding to a discharge regime ranging from C / 200 to C / 10 approximately.
    The process according to the invention can be applied to any type of lithium battery chosen from LMP batteries and Li-Po batteries, whatever the nature of the active ingredient used in the composition of the positive electrode material. . However, it is particularly suitable for LMP batteries, particularly LMP batteries in which the active material of the positive electrode is chosen from iron phosphate and its derivatives, in particular LiFePO4.
    Thus, according to a particular and preferred embodiment of the process according to the invention, the battery is a Lithium Metal Polymer battery containing LiFePO4 iron phosphate as positive electrode material.
    The present invention is illustrated by the following exemplary embodiments, to which it is however not limited.
    EXAMPLES EXAMPLE 1 Preparation of a unitary cell of an LMP battery and demonstration of the effect of the heat treatment according to the method of the invention on its physical and electrical properties
    In this example, the effect of the heat treatment according to the method of the invention has been studied on various properties of a unit cell of an LMP battery: its thickness, its internal resistance at the beginning of life, with or without step 3) overdischarge, - its discharge profile, - its capacity at the beginning of life.
    Unit cells of LMP battery were prepared. Each of the unit cells consisted of the superposition of 38 layers each containing: - a metal lithium strip (supplier Gangfeng), - 2 polymer electrolyte films, on either side of the positive electrode, - a film of positive electrode, itself consisting of a carbon-coated aluminum current collector on which has been laminated, on each side, a positive electrode material. The polymer electrolyte was obtained by extrusion of a mixture of polymers (polyethylene oxide (POE) (Zeospan), poly (vinylidene fluoride co-hexafluoropropylene) copolymer (PVDF-HFP) (Solvay), lithium salt ( lithium bis (tetrafluorosulfonylimide), LiTFSI, 3M) in mass proportions 48/40/12.
    The positive electrode material was obtained by extrusion and rolling of a mixture of lithium iron phosphate (UFePO 4) (Pulead, unless otherwise indicated), a copolymer of ethylene oxide and butylene oxide P (OE-OB) (Nippon Shokubai), and LiTFSI (3M) in mass proportions 68/24/6, and carbon (Ketjen black) 2%, on both sides of a coated aluminum current collector a carbon protection layer (ARMOR).
    Then, each of the unit cells was obtained by juxtaposing each of the films obtained previously.
    Measurements of the internal resistance of the cells tested in this example were carried out at the beginning of the discharge during the cycling, by applying the following calculation: Ri = ^ with AU the variation of potential between the state of rest and the state under current and Al the variation of the imposed current at the beginning of discharge. 1.1 Measurements of the effect of the heat treatment on the thickness of the cell The thickness of the non-cycled unit cell was measured before and after a thermal cycle comprising the following 3 steps: 1) a rise in temperature, since the temperature ambient temperature up to 80 ° C, 2) maintaining the temperature at 80 ° C for 48 hours, the cell also being subjected to a pressure of 2 bar, 3) the natural cooling of the cell to room temperature.
    A compression of the cell thickness of 140 μm was observed at the end of the thermal cycle. Since the cell is in the same state of charge and at the same temperature as in the initial state, ie before the thermal cycle is completed, this variation in thickness is attributed to an optimization of the interfaces during this process. heat treatment. 1.2. Effects of heat treatment on the evolution of internal resistance at the beginning of life without a step of over-decay
    Two unit cells of identical composition and as described above were heated until a temperature of 80 ° C was reached. One of these two cells was then immediately launched in cycling (Cycling C / 8 D / 2) (Cell C'1 comparative process not in accordance with the invention), while the other cell has previously undergone a step maintaining at 80 ° C for 72 hours, at a pressure of 2 bar, according to the process according to the invention (Cell C1 according to the invention).
    The appended FIG. 1 shows the evolution of the internal resistance (in%) of each of the cells as a function of the number of cycles. In this figure, revolution of the internal resistance of the cell C'1 not in accordance with the invention corresponds to the discontinuous line curve and that of the cell C1 according to the invention corresponds to the curve in solid line.
    These results show that the heat treatment makes it possible to stabilize the internal resistance of the cell C1 during cycling (only about 15% increase during the first 100 cycles) compared with that of the cell C'1 which undergoes on the contrary a increase of about 70% of its internal resistance during the first 100 cycles. The heat treatment thus makes it possible to improve the repeatability of the behavior of the cell during its lifetime while minimizing the increase in internal resistance during cycling. 1.3. Effects of heat treatment with step of over-decay on revolution of internal resistance at the beginning of life and capacity
    Two unit cells of identical composition and as described above were heated until a temperature of 80 ° C was reached. One of the two cells then underwent a step of overdischarge at 3A for a duration of 3h20 and then cycled (C / 8D / 2) (Cell C'2 obtained according to a method not in accordance with the invention). The other cell first underwent a holding step at a temperature of 80 ° C. for 72 hours and at a pressure of 2 bar, before undergoing in turn a step of overdischarge at 3A for a duration of 3 h 20 and then a cycling (C / 8 D / 2) (C2 cell obtained according to the process according to the invention).
    The appended FIG. 2 shows the evolution of the internal resistance (in%) of each of the cells as a function of the number of cycles. In this figure, revolution of the internal resistance of the cell C'2 not according to the invention corresponds to the high curve and that of the cell C2 according to the invention corresponds to the low curve.
    These results show that the heat treatment step according to the method according to the present invention makes it possible to greatly limit the increase in the internal resistance observed during the first 40 cycles of the cell C2.
    In addition, it is observed that the internal resistance of the cell C2 is lower than that of the cell C1 having undergone a heat treatment according to the method according to the invention but not having undergone the optional step of overdischarge (see FIG. 1). These results confirm that the overdischarge step, although optional, can further improve the properties of the cell, including decreasing the internal resistance of the battery early in life.
    In addition, the appended FIG. 3 gives the results of the evolution of the capacity obtained at D / 2, of the two cells C '2 and C2 as a function of the number of cycles. In this figure, the discharged capacity (in Ah) is a function of the number of cycles; the high curve corresponds to the cell C2 having undergone the treatment method according to the invention whereas the low curve corresponds to the cell C'2 having not undergone such treatment.
    The results presented in FIG. 3 show that the heat treatment prior to overdischarge on the cell obtained according to the process of the invention (C2) makes it possible to reach, as soon as the first cycles, the optimal performances of the cell. EXAMPLE 2 Preparation of an LMP Battery Consisting of Several Unit Cells and Evidence of the Effect of the Heat Treatment According to the Process of the Invention on Its Physical and Electrical Properties
    In this example, the impact of a heat treatment according to the process according to the invention on the performance of an LMP battery composed of 120 unit cells connected in series ("Pack") has been evaluated. Each unit cell (or module) comprising the LMP battery had the same composition as that of the unit cells used above in the tests presented in Example 1.
    Two protocols were applied on 2 identical batteries:
    Protocol 1 according to the invention: - Heating the battery from room temperature up to 80 ° C, - Heat treatment: regulation and maintenance at 86 ° C for 18h, and at a pressure of 2 bar for each of the cells, - Overdischarge at 3A.
    There was thus obtained an LMP1 battery according to the present invention.
    Protocol 2 NO according to the invention: - Heating the battery from room temperature to 80 ° C, - Overdischarge to 3A.
    There was thus obtained an LMP2 battery not in accordance with the present invention.
    The performances of each of the LMP1 and LMP2 batteries were characterized by a discharge (D / 4) and charge (C / 10) cycle.
    The gains in energy, in resistance Max / module and in total resistance (Pack) for the battery LMP1 according to the invention were calculated with respect to the values measured for each of these parameters on the battery LMP2 not according to the invention.
    The results obtained are given in Table 1 below: TABLE 1
    The treatment protocol according to the invention, that is to say including a step of maintaining the battery at the temperature of 86 ° C. for 18 hours, allows both a gain in energy and a decrease in the resistance. internally, and this as well at the level of a unit cell making up the battery as at the level of the whole battery.
    The voltage profile of the over-discharge of each of the LMP1 and LMP2 batteries is shown in the appended FIG. In FIG. 4a, the voltage (in V) is a function of the time (t in Arbitrary Units: UA) and in FIG. 4b the derivative of the profile of FIG. 4a dt / dV (in sV) is a function of the voltage (in V). In FIGS. 4a and 4b, the dashed line curves correspond to the results of the LMP1 battery according to the invention, while the solid line curves correspond to the results of the LMP2 battery not in accordance with the invention.
    The results presented in FIG. 4 show that the different shoulders are more marked for the LMP2 battery that has not undergone a heat treatment according to the method of the invention than for the LMP1 battery that has undergone it. This is all the more visible by deriving the curve at the level of the shoulder located towards 1.4 V.
    The attached FIG. 5 shows the Ragone diagram of the LMP1 and LMP2 batteries. On this diagram, the power (in kW) is a function of energy (in W.h). In this figure, the dashed curve corresponds to the LMP1 battery according to the invention and the dash curve corresponds to the LMP2 battery not in accordance with the invention.
    The same experiment was carried out on a strictly identical battery, but performing the heat treatment at a temperature of 70 ° C for 18 hours instead of 86 ° C. An LMP1 battery also according to the invention was obtained.
    The appended FIG. 6 shows the Ragone diagram of the LMP1 'and LMP2 batteries. On this diagram, the power (in kW) is a function of energy (in W.h). In this figure, the broken line curve corresponds to the battery LMP1 'according to the invention and the curve in solid line corresponds to the battery LMP2 not according to the invention.
    The Ragone diagrams of Figures 5 and 6 reveal that the heat treatment according to the method according to the invention is beneficial to all discharge regimes. The differences between the battery which has or has not undergone a heat treatment protocol according to the process according to the invention are all the more marked as the temperature is low (see FIG. EXAMPLE 3 Preparation of an LMP battery composed of several unit cells and highlighting the effect of the heat treatment according to the method of the invention on its physical and electrical properties
    In this example, the impact of an on-line heat treatment according to the process according to the invention on the performance of an LMP battery composed of 120 unit cells connected in series ("Pack") has been evaluated. Each unit cell (or module) comprising the LMP battery had the same composition as that of the unit cells used above in the tests presented in Example 1.
    Two protocols were applied on 2 identical batteries:
    Protocol 3 according to the invention: - Heating the battery from room temperature up to 80 ° C, - Heat treatment: Potentiostatic hold at 3.3V for 15 hours with regulation of the temperature at 80 ° C, under pressure 2 bars on each cell, - Overdischarge at 3A.
    There was thus obtained an LMP3 battery according to the present invention.
    Protocol 4 NOT in accordance with the invention: - Heating the battery from room temperature to 80 ° C, - Overdischarge to 3A.
    There was thus obtained an LMP4 battery not in accordance with the present invention.
    The performance of each of the LMP3 and LMP4 batteries was characterized by a discharge (D / 4) and charge (C / 10) cycle.
    The gains in energy, resistance Max / module and total resistance (Pack) for the LMP3 battery according to the invention were calculated with respect to the values measured for each of these parameters on the LMP4 battery not in accordance with the invention.
    The results obtained are given in Table 2 below: TABLE 2
    These results show that the heat treatment of the battery when it is powered up also achieves a significant improvement in the performance of the battery.
    The voltage profile of the over-discharge of each of the LMP3 and LMP4 batteries is shown in the attached FIG. In FIG. 7a, the voltage (in V) is a function of time (t in UA) and in FIG. 7b the derivative of the profile of FIG. 7a dt / dV (in sV ') is a function of the voltage ( in V). In FIGS. 7a and 7b, the dashed line curves correspond to the results of the LMP3 battery according to the invention while the solid line curves correspond to the results of the LMP4 battery not according to the invention.
    The results presented in FIG. 7 show that the different shoulders are more marked for the LMP4 battery which has not undergone a heat treatment under voltage according to the method of the invention than for the LMP3 battery that has undergone it. This is all the more visible by deriving the curve at the level of the shoulder located towards 1.4 V.
    权利要求:
    Claims (14)
    [1" id="c-fr-0001]
    A method for heat treatment of a lithium battery chosen from Lithium-Metal-Polymer (LMP) batteries and lithium-ion polymer batteries, said battery comprising at least one positive electrode, at least one polymer electrolyte and at least one negative electrode, said method being characterized in that it comprises: 1) at least a first step of bringing said battery to a temperature T1 of at least 50 ° C, 2) at least a second step in which one maintains said battery at the temperature T1 while applying a pressure of at least 0.5 bar, said steps 1) and 2) being performed before the first charge of said battery.
    [2" id="c-fr-0002]
    2. Method according to claim 1, characterized in that the temperature T1 varies from 50 to 120 ° C.
    [3" id="c-fr-0003]
    3. Method according to claim 1 or 2, characterized in that the temperature T1 varies from 70 to 105 ° C.
    [4" id="c-fr-0004]
    4. Method according to any one of the preceding claims, characterized in that during step 2), the pressure applied to the battery varies from 0.5 to 10 bar.
    [5" id="c-fr-0005]
    5. Method according to any one of the preceding claims, characterized in that during step 2), the pressure applied to the battery varies from 1 to 7 bars.
    [6" id="c-fr-0006]
    6. Method according to any one of the preceding claims, characterized in that the duration of step 2) varies from 5 hours to 1 week.
    [7" id="c-fr-0007]
    7. Method according to any one of the preceding claims, characterized in that the duration of step 2) varies from 5 to 25 hours.
    [8" id="c-fr-0008]
    8. Method according to any one of the preceding claims, characterized in that step 2) is performed under tension and in that the battery is placed in potentiostatic hold at a voltage corresponding to the initial state of charge of the battery. after assembly more or less 10%.
    [9" id="c-fr-0009]
    9. Method according to any one of the preceding claims, characterized in that step 2) is performed under tension and in that the battery is placed in potentiostatic hold at a voltage corresponding to the initial state of charge of said battery after assembly more or less 2%.
    [10" id="c-fr-0010]
    10. Method according to any one of the preceding claims, characterized in that it is applied to an LMP battery and that it further comprises a step 3) of overdischarge of said LMP battery.
    [11" id="c-fr-0011]
    11. The method of claim 10, characterized in that the step 3) of overdischarge of the LMP battery is conducted until the battery is over-discharged by 2 to 40% of its nominal capacity.
    [12" id="c-fr-0012]
    12. The method of claim 10 or 11, characterized in that the step 3) of overdischarge of the LMP battery is conducted until the battery is over-discharged by 8 to 20% of its nominal capacity.
    [13" id="c-fr-0013]
    13. Method according to any one of claims 10 to 12, characterized in that the step 3) of overdischarge is performed by applying to the battery an overdischarge current corresponding to a discharge regime ranging from C / 10 to C / 200.
    [14" id="c-fr-0014]
    14. Method according to any one of the preceding claims, characterized in that the lithium battery is an LMP battery in which the active material of the positive electrode is selected from iron phosphate and its derivatives.
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    CN109314234B|2021-10-26|
    JP2019521473A|2019-07-25|
    CN109314234A|2019-02-05|
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1655239A|FR3052599B1|2016-06-08|2016-06-08|THERMAL TREATMENT PROCESS OF A LITHIUM BATTERY|FR1655239A| FR3052599B1|2016-06-08|2016-06-08|THERMAL TREATMENT PROCESS OF A LITHIUM BATTERY|
    JP2018560019A| JP2019521473A|2016-06-08|2017-06-07|Heat treatment process of lithium battery|
    TW106118918A| TW201813168A|2016-06-08|2017-06-07|Process for heat treating a lithium battery|
    SG11201808813SA| SG11201808813SA|2016-06-08|2017-06-07|Method of heat treatment for a lithium battery|
    US16/304,886| US20200328401A1|2016-06-08|2017-06-07|Process for heat treating a lithium battery|
    EP17734787.9A| EP3469645B1|2016-06-08|2017-06-07|Method for thermally treating a lithium battery|
    KR1020187034680A| KR20190003688A|2016-06-08|2017-06-07|How to Heat Treatment Lithium Batteries|
    AU2017278454A| AU2017278454A1|2016-06-08|2017-06-07|Method of heat treatment for a lithium battery|
    CN201780035596.0A| CN109314234B|2016-06-08|2017-06-07|Heat treatment method of lithium battery|
    BR112018071967A| BR112018071967A2|2016-06-08|2017-06-07|heat treatment process of a lithium battery|
    RU2018135251A| RU2018135251A|2016-06-08|2017-06-07|METHOD FOR THERMAL TREATMENT OF LITHIUM BATTERY|
    CA3021298A| CA3021298A1|2016-06-08|2017-06-07|Method of heat treatment for a lithium battery|
    PCT/FR2017/051433| WO2017212171A1|2016-06-08|2017-06-07|Method of heat treatment for a lithium battery|
    IL263391A| IL263391D0|2016-06-08|2018-11-29|Process for heat treating a lithium battery|
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