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  • 专利说明
  • 权利要求
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    • 专利摘要:
    Use of a reversible liquid / solid phase change electrolyte for the preparation of a bipolar lithium-ion battery or accumulator characterized in that said electrolyte contains at least one block copolymer comprising at least one polymeric segment A soluble in said electrolyte and at least one polymeric segment B having a solubilization temperature "T" in said electrolyte, the polymeric segments A and B being present in amounts sufficient to allow the physical gelation of the electrolyte at a temperature greater than or equal to temperature "T".
    公开号:FR3013513A1
    申请号:FR1361395
    申请日:2013-11-20
    公开日:2015-05-22
    发明作者:Gilles Moreau；Lionel Picard
    申请人:Commissariat a lEnergie Atomique CEA；Commissariat a lEnergie Atomique et aux Energies Alternatives CEA；
    IPC主号:
    专利说明:

    [0001] TECHNICAL FIELD The present invention relates to the field of lithium electrochemical generators, which operate according to the principle of insertion or deinsertion, or in other words intercalation-deintercalation, of lithium in at least one electrode.
    [0002] It relates in particular to the field of lithium electrochemical accumulators comprising at least one current collector with bipolar function, also called bipolar batteries. More specifically, the invention aims to improve the sealing of a bipolar battery vis-à-vis its liquid electrolyte.
    [0003] STATE OF THE ART The architecture of conventional lithium-ion batteries is an architecture that can be described as monopolar because it comprises a single electrochemical cell comprising an anode, a cathode and an electrolyte.
    [0004] The architecture of this type of battery is mainly developed on a monopolar architecture integrated winding or stacking. In a monopolar winding architecture, also called "roll-to-roll" in English, the winding consists of a current collector on which is continuously deposited a positive electrode material (cathode), a material separator polymer or ceramic interposed to a negative electrode material (anode) itself deposited on another current collector. As examples of monopolar architecture winding geometry batteries, mention may be made of those disclosed in US patent application 2006/0121348, and US 7348098 and US 7338733.
    [0005] As for the architecture of conventional lithium-ion batteries stacking, also called "stack" in English, it corresponds to a stack of positive electrodes, separators and negative electrodes assembled to allow to have a large active area of material. Examples of stacked geometry batteries include those disclosed in US Patent Application Serial Nos. 2008/060189, US 2008/0057392, and US Patent 7335448.
    [0006] Monopolar architectures by winding or stacking have the significant advantage of having a large active surface of material. However, the potential difference is restricted to the unit value of the potential difference between the two electrode materials used.
    [0007] Two types of packaging, rigid or flexible, are generally considered for monopolar batteries. A rigid packaging makes it possible to withstand mechanical stresses as well as overpressures / depressions, particularly caused during its filling electrolyte, but it is massive and bulky. For its part, a flexible packaging, less dense than the rigid packaging, allows to obtain higher energy densities. It is also less resistant to external aggression. Usually, these monopolar batteries are filled with a liquid electrolyte at ambient temperature by drawing the inside of the element under vacuum and then filling at ambient temperature and pressure. It should be noted that a flexible packaging is more restrictive during filling. It is indeed more complex to fill electrolyte because more subject to pressure variations and more complex to seal. In order to increase the average potential of a monopolar Li-ion battery while maintaining a comparable energy density, batteries have been developed with a plurality of electrochemical cells in series. The architecture of the battery is thus described as bipolar because it comprises a cathode of a cell and an anode of an adjacent cell which are supported on the same current collector in the form of a plate and qualified itself as bipolar electrode. A bipolar battery thus puts in series several monopolar accumulators via the electrodes or bipolar current collectors. Numerous patent applications or patents relating to such bipolar batteries, such as US 7279248, US 7220516, US 7320846, US 7163765, WO 03/047021, WO 2006/061696, US 7097937, U52007 / 00115047, can be cited here. The main advantages of bipolar batteries are to have a reduced electrical resistance, compared to monopolar accumulators connected in series by external connectors, to have a reduced mass and not to contain unnecessary volumes, that is to say say that the package containing the battery does not include substantially empty spaces. A bipolar battery is also in flexible format, because its own electrodes are used for inter compartmental sealing.
    [0008] The main technical problem encountered during the manufacture of bipolar batteries is to make compartments, corresponding to the electrochemical cells, and also called "unitary elements" which are sealed with respect to each other with respect to the liquid electrolyte qu 'they contain. For obvious reasons, it is necessary to avoid leaks. A poor seal between the different compartments will inevitably cause a malfunction of the bipolar battery by ionic short circuits. Conventional filling methods are therefore confronted with the need to make compartments perfectly impervious to liquid electrolyte and not containing entrapped gases.
    [0009] Several solutions have already been envisaged for improving the filling of bipolar batteries with electrolyte. Usually, the method of filling a battery requires evacuation of the package containing the anode / separator / cathode assembly, and the introduction of the liquid electrolyte, under pressure or not. These operations are generally followed by an impregnation time to allow the electrolyte to fill all the void zones, or pores, of the anode / separator / cathode assembly. The sealing operation is conventionally performed consecutively to ensure the integrity of the system. It is generally performed by welding or applying a patch to the package containing the anode / separator / cathode / electrolyte assembly. Unfortunately, there is an inhomogeneity of material between the inserts and the packaging, detrimental to the seal. Moreover, such a method is complex to implement in the case of a bipolar element. The current collectors acting packaging, the performance of the battery can indeed be deteriorated during the filling and sealing steps.
    [0010] The other solutions proposed in JP 2008166256, US 2009/0282672 and TW 201044674 also have the disadvantage of leading to a non-homogeneous seal that is to say degraded. Of course, other solutions, in particular those disclosed in JP 2008130450 and US 7163765, make it possible to overcome the problem of non-homogeneous sealing. However, these solutions remain on the other hand too complex in terms of implementation.
    [0011] Consequently, there remains a need for an effective solution to guarantee a homogeneous, long-lasting and easy-to-use seal, in the context of the filling of the electrolyte in bipolar batteries in particular. The present invention precisely aims to meet this need.
    [0012] In particular, the object of the invention is to propose an improved solution for producing, in a bipolar Li-ion battery, and more generally in a lithium electrochemical generator, the filling of the electrolyte while making it possible to guarantee the tightness of the compartments to each other vis-à-vis the liquid electrolyte.
    [0013] SUMMARY OF THE INVENTION The main subject of the present invention is the use of a liquid / solid reversible phase change electrolyte for the preparation of a bipolar lithium-ion battery or accumulator in which the said electrolyte contains at least one copolymer. block reactor comprising at least one polymeric segment A soluble in said electrolyte and at least one polymeric segment B having a solubilization temperature "T" in said electrolyte, the polymeric segments A and B being present in amounts sufficient to allow gelation Physics of the electrolyte at a temperature greater than or equal to the temperature "T". Said block copolymer is said to be thermosensitive. Thus, the copolymer considered according to the present invention advantageously provides an increase in the viscosity, or even gelation of the electrolyte for lithium-ion battery, when it is brought to a temperature at least equal to the temperature "T", then the return of the electrolyte to a liquid state when the temperature of the battery falls below "T". It is for this reason that the electrolyte is called "reversible liquid / solid phase change".
    [0014] This ability of the copolymer according to the invention is essentially linked to the presence of at least one polymeric segment (B) which is insoluble in the electrolyte at a temperature below "T" but which becomes soluble at the temperature "T". ". Without wishing to be bound by any theory, it seems that the solubilization of this polymeric segment in the electrolyte, obtained at a temperature greater than "T", leads to a development of the chains constituting this polymeric segment thus allowing by physical interactions between the chains of the polymeric segments B or between the chains of the polymeric segments B and the polymeric segments A, and thus forming a three-dimensional network, by physical crosslinking, creating strong bonds, for example hydrogen bonds. On the other hand, at a temperature below "T", these polymeric segments B are insoluble in the electrolyte, and consequently their chains are folded back on themselves, coiled.
    [0015] Admittedly, a use of block copolymers has already been considered in lithium batteries, but, to the knowledge of the inventors, essentially to improve the ionic conductivity of these batteries. These applications are described in particular in documents WO 2010/101794, WO 2009/131961 and WO 2007/142731. Moreover, the copolymers described therein are different from those considered according to the invention.
    [0016] The present invention also relates to a method for producing a lithium battery or accumulator comprising at least one electrochemical cell (C) consisting of at least one anode and a cathode on either side of an impregnated separator an electrolyte, and a compartment arranged to contain the electrochemical cell (s) with sealing while being traversed by a portion of the current collectors forming the poles, in this process: said electrolyte is at a change of reversible liquid / solid phase and contains at least one block copolymer comprising at least one polymeric segment A soluble in said electrolyte and at least one polymeric segment B having a solubilization transition temperature "T" in said electrolyte, the polymeric segments A and B being present in amounts sufficient to allow the physical gelation of the electrolyte at a temperature greater than or equal to the temperature "T" and said process comprises at least the steps of: - manipulating said electrolyte during the elaboration of said cell at a temperature greater than or equal to the temperature "T" and - lowering the temperature of said electrolyte, resulting from the sealing of said cell containing said gel electrolyte at a temperature below the temperature T.
    [0017] The method according to the invention is advantageous in several ways for the production of a lithium battery or accumulator comprising a stack of several that is to say at least two electrochemical cells (C).
    [0018] Thus, it advantageously allows rapid assembly of the gelled electrolyte "hot" in the restricted volume of the compartment, also called "caisson". The return of the electrolyte in its liquid form makes possible a homogeneous impregnation of the separator.
    [0019] Finally, at a temperature below the temperature "T", and in particular at room temperature, the electrolyte returns to its optimum characteristics of use in a bipolar Li-ion battery. The proposed method of assembly according to the invention therefore provides a perfect seal, an independent mechanical strength related to the internal vacuum conditions of the element, as well as a perfect impregnation thanks to the internal vacuum conditions of 1 ' element. Other advantages and characteristics will appear on reading the description and the figures that follow.
    [0020] Description of the Figures - Figure 1 shows a diblock copolymer, in a) is shown the basic diblock consisting of the polymeric segment A (clear) and polymeric segment B (dark), in b) is shown the diblock at a temperature below "T": the polymeric segment A (clear) is deployed and the polymeric segment B (dark) is in folded / curled form, in c) is shown the diblock at a temperature greater than "T": the polymeric segment A (clear ) and polymeric segment B (dark) are in unfolded form. - Figure 2 shows a triblock copolymer, in a) is represented the basic triblock consisting of the polymeric segment A (clear), the polymeric segment B (dark) and the polymeric segment C (black), in b) is represented the triblock at a temperature below "T": the polymeric segment A is deployed, while the polymeric segments B and C are in folded / curled form, in c) the triblock is represented at a temperature greater than "T": the polymeric segments A and B are in unfolded form while the polymeric segment C is in folded / curled form. - Figure 3 shows the behavior of the diblock copolymers as a function of temperature. Scheme a) represents the behavior of the diblock copolymers at a temperature below T: the polymeric segments A (clear) are deployed and the polymeric segments B (dark) are in folded / coiled form. In this configuration, the electrolyte is liquid that is to say that the viscosity of the electrolyte is not changed. Scheme b) shows the behavior of the diblock copolymers at a temperature above T: the polymeric segment A (clear) and the polymeric segment B (dark) are in unfolded form. In this configuration, the electrolyte is in gelled form. FIG. 4 represents the behavior of the triblock copolymers as a function of the temperature. Scheme a) represents the behavior of the triblock copolymers at a temperature below T: the polymeric segments A are deployed while the polymeric segments B and C are in folded / coiled form. In this configuration, the electrolyte is liquid that is to say that the viscosity of the electrolyte is not changed. Scheme b) represents the behavior of the triblock copolymers at a temperature above T: the polymeric segments A and B are in unfolded form while the polymeric segments C are in folded / coiled form. In this configuration, the electrolyte is in gelled form. FIG. 5 represents a method for producing bipolar elements for "stacked" architecture battery. FIG. 6 represents a method for producing bipolar elements for "winding" architecture battery. Definitions By "soluble" polymer in FIG. a solvent, within the meaning of the present invention, is understood to mean a polymer which, at a concentration of 0.1% by weight of active material in said solvent at 25 ° C., gives a macrocospically homogeneous, transparent or translucent solution or suspension that is, having a transmittance value at a wavelength of 500 nm through a 1 cm thick sample of at least 70%, preferably 80%. By "heat-sensitive" polymer in the sense of the present invention is meant a polymer whose properties, particularly vis-à-vis the viscosity, will vary depending on the temperature. The "heat-sensitive" nature of the polymers used according to the invention is essentially due to the presence of the polymeric segment (B) which has a solubilization temperature "T". The temperature "T" designates in the context of the invention the temperature of change of state of the electrolyte. From this temperature, the electrolyte favors a gelled state and below this temperature, it is liquid. For the purposes of the present invention, the term "solubilization temperature" means a temperature above which said polymer is soluble in the medium used in particular in the electrolyte used.
    [0021] DETAILED DESCRIPTION I - Thermosensitive Copolymer As mentioned above, the block copolymer used in the present invention comprises at least one polymeric segment A soluble in said electrolyte, at least one polymeric segment B having a solubilization temperature "T" in said electrolyte and where appropriate, at least one polymeric segment C. The polymeric segments (A), (B) and (C) are therefore different in nature. For obvious reasons, the nature and the length of each of the polymeric segments considered respectively for (A), (B) and (C) are chosen as a function of the desired properties and in particular as a function of the chosen electrolyte, in particular the segments Polymers can be amphiphilic or very similar in nature.
    [0022] Similarly, the block copolymer used according to the invention is advantageously electro-inactive. It thus has substantially no effect on the performance of the battery under normal conditions of use, and in particular when the temperature of the battery is lower than "T", especially at room temperature.
    [0023] Polymeric segment A As previously mentioned, the polymeric segment A is soluble in said electrolyte whatever the temperature, in particular it is soluble at a temperature below "T".
    [0024] Advantageously, the polymeric segment A has a molar mass ranging from 2,000 g.mol -1 to 300,000 g.mol -1, preferably from 8,000 g.mol -1 to 80,000 g.mol -1 -1. Preferably, the polymeric segment A has a degree of polymerization DPA greater than 10, preferably greater than 20, more particularly ranging from 50 to 800.
    [0025] Any polymer soluble in the electrolyte used can be used as polymeric segment A. According to one preferred embodiment, the polymeric segment A is chosen from the following polymers: polyacrylates, polymethacrylates, polycarbonates, polyestercarbonates, polylactones, polylactams, polyesters, polyethers, soluble homopolymers and random copolymers of polyethers, in particular polyoxyethylene, polyoxypropylene, polyoxybutylene, as well as copolymers of these corresponding polymers or monomers. The polymeric segment A may therefore consist of monomers of the same nature or of monomers of different nature.
    [0026] According to a particularly preferred embodiment, the polymeric segment A is represented by a polymer chosen from polycarbonates, polyethers and their copolymers. Polymeric Segment B The block copolymer used in the present invention further comprises at least one polymeric segment B having a solubilization temperature "T" in said electrolyte.
    [0027] Preferably, the polymeric segment B has a molar mass ranging from 2,000 g.mol -1 to 300,000 g / mol, preferably from 8,000 g / mol to 80,000 g / mol. Preferably, the polymeric segment B has a degree of polymerization DPB greater than 10, preferably greater than 20, more particularly ranging from 50 to 800.
    [0028] According to a preferred embodiment, the polymeric segment B is a polymer obtained from at least one monomer chosen from the following monomers: acrylic and methacrylic acids, N-alkyl-acrylamides or N-alkyl-methacrylamides, in particular N isopropylacrylamide, N-isopropylmethacrylamide, N, N'diethylacrylamide, saccharides, vinylidene fluoride, hexafluoropropylene.
    [0029] According to a particularly preferred embodiment, the polymeric segment B is a polymer chosen from poly (N-alkyl-acrylamides), poly (N-alkyl-methacrylamides), polysaccharides, polyvinylidene fluoride (PVdF) and polyvinylidene fluoride copolymers. hexafluoropropylene (PVdF-HFP). Advantageously, the molar ratio of polymeric segments B / polymeric segments A is greater than 0.5, and preferably ranges from 1 to 10 and more preferably from 2 to 5. Polymeric segment C Advantageously, the block copolymer further comprises at least one polymeric segment C insoluble in the electrolyte. More specifically, the polymeric segment C is insoluble in the electrolyte whatever the temperature, in particular it is insoluble at a temperature greater than "T". Without wishing to be bound to any theory, the polymeric segment C contributes to the creation of crosslinking nodes which will stabilize the network formed by the block copolymers and thus improve the structure of the gel. The polymeric segment C thus makes it possible to increase the elastic modulus of the gel. In addition, the presence of polymeric segments C in the block copolymer makes it possible to use said block copolymer in the electrolyte in a lesser quantity without the stability of the electrolyte in gelled form being impaired.
    [0030] Preferably, the polymeric segment C is chosen from saturated or unsaturated polyolefins, branched or non-branched, in particular C2-C12, polystyrene and mixtures thereof and copolymers thereof.
    [0031] Advantageously, the molar ratio of polymeric segments A to polymeric segments C is from 0.5 to 10, preferably from 1 to 5. Advantageously, the molar ratio of polymeric segments B to polymeric segments C is from 1 to 10, preferably from 1 to 3. The copolymers with blocks according to the invention can be obtained by radical, anionic or cationic controlled polymerization (ATRP (Atom-transfer radical polymerization), ITRP (iodine-transfer radical polymerization), RAFT (reversible Addition fragmentation chain transfer) ...). These types of polymerization make it possible to obtain a specific geometry of the block copolymer, depending on the properties targeted. It is indeed possible to envisage choosing the polymeric segments in order to obtain a modification of the properties of said block copolymer following a modification of pKa or pKb. The block copolymer used according to the invention can thus be an alternating block, statistical, comb copolymer. The accompanying Figures 1-4 show several variants of block copolymers suitable for the invention. II - Electrolyte According to a preferred embodiment, the block copolymer (s) is / are present in an amount ranging from 1 to 25% by weight and preferably from 10% to 20% by weight relative to the total weight of the 'electrolyte. The electrolyte used according to the invention comprises at least one lithium salt. The lithium salts can be chosen from all the lithium compounds which can be dissociated into an organic solvent in order to produce lithium ions. By way of examples of these lithium compounds, there may be mentioned LiC104, LiBF4, LiPF6, LiCF3SO3, LiN (CF3SO2) 2. The electrolyte used according to the invention may comprise any organic solvent generally used for the manufacture of lithium electrochemical accumulator, in particular the solvent is chosen from ethylene carbonate, propylene carbonate, dimethyl carbonate and carbonate. ethylmethyl, diethyl carbonate, tetrahydrofuran, tetraethylene glycol dimethyl ether, dimethyl ether, dioxolane, dioxane, polyethylene glycol dimethyl ether and or nitriles. As is apparent from the foregoing, the polymeric segment (B) is chosen to adjust the temperature "T", which conditions the change in viscosity, to a value beyond which the electrolyte can be easily manipulated, Particularly viscous enough not to sink during filling of the cell without presenting risks for the operator including burns or toxic fumes. Advantageously, said electrolyte is manipulated, during the preparation of said battery or said accumulator, at a temperature above the temperature "T", advantageously ranging from "T" to "T" + 20 ° C. Advantageously, the temperature "T" is less than or equal to 80 ° C, preferably "T" ranges from 40 ° C to 80 ° C, preferably from 60 to 80 ° C and more preferably from 70 ° C to 80 ° C . Preferably, the electrolyte in gelled form has a shear strength modulus G 'greater than 500 Pa and a shear loss modulus G "less than G. Also, the electrolyte has a Cl conductivity varying from 10 -4 S.cm-1 to 0.1S.cm-1 at a temperature below T, that is to say when it is in liquid form III - Method The invention also relates to a process for the production of a lithium battery or accumulator comprising at least: - an electrochemical cell (C) consisting of at least one anode and a cathode, the anode and the cathode forming part of a bipolar electrode, located on both sides; Another of an electrolyte impregnated with a separator, and a compartment arranged to contain the electrochemical cell (s) with sealing and traversed by a portion of the current collectors forming the poles. the electrolyte considered according to the invention, that is to say with wherein at least one thermosensitive copolymer is manipulated in the form of a gelled layer which is deposited on the surface of said anode or cathode. Advantageously, the gelled electrolyte layer already integrates the separator to form the "separator / electrolyte" assembly.
    [0032] Preparation of the "separator / electrolyte" assembly Two embodiments can be envisaged for the preparation of this assembly according to the architecture considered for the cell, namely "stacking" or "winding". According to a first variant, preferred in the case of a "stacking" architecture, the method comprises a step of proceeding, at a temperature above the temperature "T" advantageously ranging from "T" to "T" + 20 ° C, depositing said gelled electrolyte on at least one surface of a separator in an amount sufficient to form a supported layer. Advantageously, this deposition step of the gelled electrolyte layer is carried out in a mold in which at least one separator generally in the form of a sheet or ribbon has been previously deposited. According to a second variant, preferred in the case of a "winding" architecture, the method according to the invention comprises a step of depositing, by coating or spraying on the separator under consideration, the gelled electrolyte. This deposition is carried out at a temperature greater than "T", advantageously ranging from "T" to "T" + 20 ° C. The separator is generally in the form of a ribbon or sheet. In more detail, the method for producing an electrochemical cell according to the invention comprises at least the steps of: (a) preparing a unitary element by assembling a positive electrode (cathode), of the separator assembly electrolyte "and a negative electrode (anode), (b) to put the unitary element under vacuum, (c) to seal the unitary element by performing an air vacuum in a box, and (d) restoring the unit element at atmospheric pressure and ambient temperature. At ambient temperature, that is to say a temperature below "T", the electrolyte is in liquid form, therefore, this step makes it possible to perform the impregnation of the separator as well as the mechanical stressing of the electrolyte. unitary element.
    [0033] Generally, the cathode considered in step (a) is the positive part of a current collector, called current collector 1, and the anode used is more exactly the negative part of a current collector adjacent to the current collector 1 Advantageously, step (b) is carried out in a volume box-type package adapted to the size of the final stack corresponding to the set of unitary elements. The use of a box of adapted volume makes it possible to carry out the stacking by minimizing the empty space between the stack and the box. In step (c), it can be noted that the filling is always performed before complete sealing of the element. Several sealing modes are compatible with the fact of working under vacuum including mechanical sealing, heat sealing, heat sealing, ultrasonic welding, UV baking ... The volume of the box, adapted to the size of the stack, also allows to minimize the stress related to the pressure between the inside and the outside of the unitary element, sealing can be achieved for example by cold compression, hot, under UV. The production of a battery comprising "n" stacks is performed by repeating "n" times the steps mentioned above, "n" ranging from 2 to 200. When producing the unit elements 2 to "n-1", two bipolar electrodes are used. When producing the unit elements 1 and "n", a terminal electrode and a bipolar electrode are used. Embodiments 1 and 2 appearing below show methods for producing a battery comprising an electrolyte according to the invention, that is to say gelled "hot" more precisely gelled at a temperature above "T" . The battery is sealed by using a vacuum chamber of reduced volume. The examples which follow illustrate the invention without limiting its scope. Example 1 Preparation of a bipolar cell by stacking with an electrolyte according to the invention. This process is illustrated in FIG. 5 in which steps 1 to 5 are presented successively from top to bottom.
    [0034] Step 1 - Gelation of the electrolyte and its additive (copolymer) in a suitable mold, at a temperature above "T" particularly from 40 ° C to 80 ° C. The quantity of electrolyte is adapted to the needs of the battery element. The presence of the separator in the mold makes it possible to obtain a "separator / electrolyte" assembly in solid form. Step 2 - Implementation of a stacked unitary stack assembly electrode / set "separator / electrolyte" / electrode, in temperature conditions greater than "T", to obtain a bipolar element. Step 3 - Establishment of a sealing system of the bipolar element under vacuum to avoid the presence of air in the system under high temperature conditions. Step 4 - Iteration of the assembly and sealing step (steps 2 and 3) to manufacture the number of compartments as necessary to obtain the desired battery under high temperature conditions. Step 5 - Restore the sealed assembly to ambient temperature to allow the electrolyte to recover its optimal properties and obtain a functional bipolar battery. Example 2 Preparation of a bipolar coil cell with the aid of an electrolyte according to the invention. This process is illustrated in FIG. 6 in which steps 1 to 5 are presented successively from top to bottom. Step 1 - Shaping of an electrolyte / separator assembly using the viscous characteristics of the electrolyte and its additive (copolymer) at a temperature above "T" particularly from 40 ° C to 80 ° C so as to obtain a flexible sheet "separator / electrolyte" windable. At the end of this step, a "wound" separator / electrolyte assembly is obtained. Step 2 - Implementation of an electrode assembly / "separator / electrolyte" assembly / electrode under high temperature conditions. The manufacturing method used is a system of lamination and distribution of elements of the "roll to roll" type to allow a facilitated realization of the unitary elements.
    [0035] Step 3 - Establishment of a sealing system of the bipolar element under vacuum to avoid the presence of air in the system under high temperature conditions. Step 4 - Iteration of the assembly and sealing step (steps 2 and 3) to manufacture the number of compartments as necessary to obtain the desired battery under high temperature conditions. Step 5 - Restore the sealed assembly to ambient temperature to allow the electrolyte to recover its optimal properties and obtain a functional bipolar battery.
    [0036] The methods of preparation of Examples 1 and 2 were carried out with a copolymer formed of the following polymeric segments A, B and C: Segment A: polyacrylate (10000 g.mol -1) Segment B: poly (n-butyl methacrylamide (50000 g.mol -1) Segment C: Polyethylene (15000g · mol1-1).
    [0037] The mixture: EC / PC / DMC (1/1/3) .01 + 1M LiTFSI (LiN (CF3502) 2) is used as the electrolyte. The solubilization temperature "T" of the polymer segment B corresponding to the gelation of the electrolyte being equal to 80 ° C.
    权利要求:
    Claims (23)
    [0001]
    REVENDICATIONS1. Use of a reversible liquid / solid phase change electrolyte for the preparation of a bipolar lithium-ion battery or accumulator characterized in that said electrolyte contains at least one block copolymer comprising at least one polymeric segment A soluble in said electrolyte and at least one polymeric segment B having a solubilization temperature "T" in said electrolyte, the polymeric segments A and B being present in amounts sufficient to allow the physical gelation of the electrolyte at a temperature greater than or equal to temperature "T".
    [0002]
    2. Use according to claim 1 characterized in that said electrolyte is manipulated, during the preparation of said battery or said accumulator, at a temperature above the temperature "T", preferably ranging from "T" to "T" +20 ° C.
    [0003]
    3. Use according to one of the preceding claims characterized in that the temperature "T" varies from 40 ° C to 80 ° C.
    [0004]
    4. Use according to one of the preceding claims wherein the electrolyte in gelled form has a shear conservation modulus G 'greater than 500 Pa and a shear loss modulus G "less than G'.
    [0005]
    5. Use according to one of claims 1 to 4 wherein the electrolyte has a conductivity C1 ranging from 10-4 S.cm-1 to 0.1S.cm-1 at a temperature below T.
    [0006]
    6. Use according to one of the preceding claims wherein the block copolymer comprises at least one polymeric segment A of molar mass ranging from 2000 g.mo1-1 to 300 000 g.mo1-1 preferably 8000 g.mo1 -1 to 80,000 g.mo1-1.
    [0007]
    7. Use according to one of the preceding claims wherein the block copolymer comprises at least one polymeric segment A having a degree of polymerization DPA greater than 10, preferably greater than 20, more particularly from 50 to 800.
    [0008]
    8. Use according to one of the preceding claims wherein the block copolymer comprises at least one polymeric segment A selected from the following polymers: polyacrylates, polymethacrylates, polycarbonates, polyestercarbonates, polylactones, polylactams, polyesters, polyethers, homopolymers and soluble statistical copolymers polyethers, in particular polyoxyethylene, polyoxypropylene, polyoxybutylene, as well as copolymers of these corresponding polymers or monomers.
    [0009]
    9. Use according to one of the preceding claims wherein the block copolymer comprises at least one polymeric segment B of molar mass ranging from 2000 g.mo1-1 to 300 000 g.mo1-1 preferably 8000 g.mo1 -1 to 80,000 g.mo1-1. 10
    [0010]
    10. Use according to one of the preceding claims wherein the block copolymer comprises at least one polymeric segment B having a degree of polymerization DPB greater than 10, preferably greater than 20, more particularly from 50 to 800.
    [0011]
    11. Use according to one of the preceding claims wherein the block copolymer comprises at least one polymeric segment B obtained from at least one monomer selected from the following monomers: acrylic and methacrylic acids, N-alkyl- acrylamides or N-alkyl-methacrylamides, in particular Nisopropylacrylamide, N-isopropylmethacrylamide, N, N 'diethylacrylamide, saccharides, vinylidene fluoride, Hexafluoropropylene. 20
    [0012]
    12. Use according to the preceding claim wherein the block copolymer comprises at least one polymeric segment B is a polymer selected from poly (N-alkyl-acrylamides), poly (N-alkyl-methacrylamides), polysaccharides, polyfluoride. vinylidene and polyfluoride copolymers of vinylidene hexafluoropropylene. 25
    [0013]
    13. Use according to one of the preceding claims wherein the block copolymer comprises at least one polymeric segment A and at least one polymeric segment B, the molar ratio of polymeric segments B / polymeric segments A being greater than 0.5, and preferably ranging from from 1 to 10 and more preferably from 2 to 5.
    [0014]
    14. Use according to one of the preceding claims wherein the block copolymer comprises at least one polymeric segment C insoluble in the electrolyte.
    [0015]
    15. Use according to claim 14 wherein the block copolymer comprises at least one polymeric segment C selected from saturated or unsaturated polyolefins, branched or non-branched, in particular C2-C12, polystyrene and mixtures thereof and copolymers thereof.
    [0016]
    16. Use according to claim 14 or 15 comprising a block copolymer in which the molar ratio of polymeric segments A / polymeric segments C ranges from 0.5 to 10, preferably from 1 to 5.
    [0017]
    17. Use according to one of claims 14 to 16 comprising a block copolymer in which the molar ratio of polymeric segments B / polymeric segments C ranges from 1 to 10, preferably from 1 to 3.
    [0018]
    18. Use according to one of the preceding claims wherein the (s) block copolymer is / are present in an amount ranging from 1 to 25% by weight and preferably from 10% to 20% by weight relative to the total weight of the electrolyte.
    [0019]
    19. A method of producing a lithium battery or accumulator comprising at least one electrochemical cell (C) consisting of at least one anode and a cathode on either side of a separator impregnated with an electrolyte. , and a compartment arranged to contain the electrochemical cell (s) sealed while being traversed by a portion of the current collectors forming the poles characterized in that said electrolyte is reversible phase liquid / solid and contains at least one block copolymer comprising at least one polymeric segment A soluble in said electrolyte and at least one polymeric segment B having a solubilization transition temperature "T" in said electrolyte, the polymeric segments A and B being present in quantities sufficient to allow the physical gelation of the electrolyte at a temperature greater than or equal to the temperature "T" and said process d comprises at least the steps of - manipulating said electrolyte during the elaboration of said cell at a temperature greater than or equal to the temperature "T" and - lowering the temperature of said electrolyte, after the completion of sealing said cell containing said gelled electrolyte at a temperature below the temperature T.
    [0020]
    20. Method according to the preceding claim wherein said electrolyte is implemented in the form of a gelled layer which is deposited on the surface of said anode or cathode.
    [0021]
    21. Method according to the preceding claim wherein the gelled layer of said electrolyte already integrates said separator.
    [0022]
    22. The method of claim 21 wherein the gelled electrolyte / separator assembly is obtained by coating / spraying said gelled electrolyte on the separator.
    [0023]
    23. Method according to one of claims 19 to 22 comprising a stack of several electrochemical cells (C).
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    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    JP2007048541A|2005-08-09|2007-02-22|Nissan Motor Co Ltd|Electrolyte structure and its manufacturing method|
    WO2007142731A2|2006-04-04|2007-12-13|The Regents Of The University Of California|High elastic modulus polymer electrolytes|
    WO2010101794A1|2009-03-06|2010-09-10|Seeo, Inc|High ionic conductivity electrolytes from block copolymers of grafted poly|
    JP2010244943A|2009-04-08|2010-10-28|Nissan Motor Co Ltd|Bipolar secondary battery|
    WO2002033767A1|2000-10-13|2002-04-25|Matsushita Electric Industrial Co., Ltd.|Flat square battery|
    SE520007C8|2001-09-19|2006-05-16|Nilar Europ Ab|A bipolar battery, a method of manufacturing a bipolar battery and car plate composition|
    FR2832859B1|2001-11-28|2004-01-09|Commissariat Energie Atomique|LITHIUM ELECTROCHEMICAL GENERATOR COMPRISING AT LEAST ONE BIPOLAR ELECTRODE WITH ALUMINUM OR ALUMINUM ALLOY CONDUCTIVE SUBSTRATES|
    US7338733B2|2002-04-30|2008-03-04|Sanyo Electric Co., Ltd.|Battery pack|
    US7335448B2|2002-05-30|2008-02-26|Matsushita Electric Industrial Co., Ltd.|Lithium ion secondary battery|
    JP4144312B2|2002-10-08|2008-09-03|日産自動車株式会社|Bipolar battery|
    JP4135473B2|2002-11-07|2008-08-20|日産自動車株式会社|Bipolar battery|
    US7445869B2|2003-05-09|2008-11-04|Nilar International Ab|Gasket, a bipolar battery and a method for manufacturing a bipolar battery with such a gasket|
    JP4155054B2|2003-02-18|2008-09-24|日産自動車株式会社|Bipolar battery|
    JP4238645B2|2003-06-12|2009-03-18|日産自動車株式会社|Bipolar battery|
    DE10345100B4|2003-09-26|2012-03-29|Austriamicrosystems Ag|Differential amplifier configuration|
    JP4552475B2|2004-03-24|2010-09-29|Ｔｄｋ株式会社|Composite particle for electrode, electrode and electrochemical element, and method for producing composite particle for electrode, method for producing electrode, and method for producing electrochemical element|
    JP4324794B2|2004-11-09|2009-09-02|ソニー株式会社|Negative electrode active material and secondary battery|
    JP5098150B2|2004-12-07|2012-12-12|日産自動車株式会社|Bipolar battery and manufacturing method thereof|
    JP4736580B2|2005-07-12|2011-07-27|日産自動車株式会社|Bipolar battery, battery pack and vehicle equipped with these batteries|
    JP4251204B2|2006-08-31|2009-04-08|日産自動車株式会社|Battery module|
    JP5114036B2|2006-09-08|2013-01-09|Ｎｅｃエナジーデバイス株式会社|Manufacturing method of stacked battery|
    JP5119652B2|2006-11-22|2013-01-16|日産自動車株式会社|Method for manufacturing bipolar battery|
    JP5315653B2|2006-12-08|2013-10-16|日産自動車株式会社|Bipolar battery manufacturing method|
    WO2009131961A2|2008-04-21|2009-10-29|Seeo, Inc.|Proteted lithium metal electrodes for rechargeable batteries|
    TWI364129B|2009-06-08|2012-05-11|Chung Hsin Elec & Mach Mfg|Self-clinching battery structure|
    KR101137374B1|2010-01-28|2012-04-20|삼성에스디아이 주식회사|Negative active material containing super-conductive nanoparticle coated with high capacity negative material and lithium battery comprising same|
    JP5796367B2|2011-06-22|2015-10-21|日産自動車株式会社|Separator with heat-resistant insulation layer|
    FR3013512B1|2013-11-20|2021-04-23|Commissariat Energie Atomique|LI-ION BATTERY ELECTROLYTE ADDITIVE|CN105934838B|2014-02-14|2018-10-09|日本瑞翁株式会社|The porous film composition of secondary cell, secondary cell perforated membrane and secondary cell|
    CN106531971A|2016-12-12|2017-03-22|上海航天电源技术有限责任公司|Intelligent high-safety lithium-on battery with polymer skeleton|
    KR101993528B1|2017-11-03|2019-06-26|인하대학교 산학협력단|Physically crosslinked ion gel and preparation method of the same|
    KR102018881B1|2017-12-22|2019-09-06|인하대학교 산학협력단|Super capacitor and preparation method thereof|
    US10886561B2|2018-05-16|2021-01-05|City University Of Hong Kong|Adaptable electrical component|
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    法律状态:
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    优先权:
    申请号 | 申请日 | 专利标题
    FR1361395A|FR3013513B1|2013-11-20|2013-11-20|COPOLYMER FOR BIPOLAR BATTERY|FR1361395A| FR3013513B1|2013-11-20|2013-11-20|COPOLYMER FOR BIPOLAR BATTERY|
    PCT/IB2014/066100| WO2015075620A1|2013-11-20|2014-11-17|Copolymer for bipolar battery|
    US15/037,810| US10044068B2|2013-11-20|2014-11-17|Copolymer for bipolar battery|
    EP14812634.5A| EP3072177B1|2013-11-20|2014-11-17|Copolymer for bipolar battery|
    JP2016532559A| JP2016537784A|2013-11-20|2014-11-17|Copolymers for bipolar batteries|
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