• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention relates to a solid electrolyte comprising a nitrogen-free LixPOy layer with 3.6 ≤ x ≤ 6.3 and 1.5 ≤ y ≤ 4 and whose ionic conductivity is greater than or equal to 10 -5 S / cm. The invention also relates to a microbattery comprising a solid electrolyte layer. The invention will find application in the field of microbatteries and in particular for microbatteries "all solid" to improve their power. It can also find its application for electrochromes.
    公开号:FR3020503A1
    申请号:FR1453710
    申请日:2014-04-24
    公开日:2015-10-30
    发明作者:Van-Jodin Lucie Le；Arnaud Claudel；Steve Martin；Christophe Secouard
    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 a solid electrolyte for microbatteries, a microbattery comprising said solid electrolyte and a method of manufacturing said electrolyte.
    [0002] The invention will find application in the field of microbatteries and in particular for microbatteries "all solid" to improve their power. It may also find application in other fields using solid electrolytes and in particular in the field of electrochromes. Indeed, electrochromic thin film can use the same materials as microbatteries. STATE OF THE ART "All-solid" microbatteries are electrochemical components for energy storage of reduced size. Typically of a thickness less than 15pm.
    [0003] They are manufactured using technologies borrowed from microelectronics. The specificity of "all-solid" batteries is to have a solid electrolyte. The most common electrolyte used in microbatteries is LiPON. It is an amorphous material composed of lithium, phosphorus, oxygen and nitrogen. This compound is described in Bates et al. J. Pow. Sou. 43-44 (1993) 103-110 and in US-A-5338625. The precise compound described by Bates is LixPOyNz with x-2.8, 0.16 <z <0.46, 2y = 3z -7.8. Its conductivity is given at 1.6x10-6 S / cm. Numerous publications highlight the important role of the chemical composition of the electrolyte on the performance of microbatteries. The most widely accepted parameter is that increasing the N / P ratio increases the ionic conductivity. Bates shows that Li27PO3 g has a conductivity of 7.10-85 / cm whereas Li29P033N0 46 has a conductivity of 3.3x10-6S / cm. However, it is still necessary to improve the performance of the microbatteries to meet the new applications thereof including RF-ID tags, smart card, memory ... SUMMARY OF THE INVENTION The present invention proposes for this purpose an electrolyte solid comprising a layer comprising LixPOy comprising no nitrogen and whose lithium and oxygen levels are controlled to be such that 3.6 x 6.3 and 1.5 y 4.
    [0004] Advantageously, it has been observed that a solid electrolyte according to the invention has an ionic conductivity greater than or equal to 10-5S / cm. Increasing the ionic conductivity of the electrolyte essentially makes it possible to improve the power handling of the batteries. It is possible to work with higher currents without losing capacity. The invention thus makes it possible to significantly improve the performance of microbatteries. Optionally, the invention may furthermore have at least any of the following characteristics taken separately or in combination: In another aspect, the invention relates to a microbattery comprising at least one electrolyte layer as described hereinabove. above. A microbattery according to the invention has improved performance. In another aspect, the invention relates to a method of manufacturing an electrolyte as described above comprising a step of physical vapor deposition (PVD for Physical Vapor Deposition) from a sprayed Li3PO4 target. under nitrogen to obtain a layer comprising Li, P0y, nitrogen-free, with 3.6 x 6.3 and 1.5 y 4. This process advantageously allows not to deposit nitrogen in the layer of electrolyte. BRIEF DESCRIPTION OF THE FIGURES The objects, objects, as well as the features and advantages of the invention will emerge more clearly from the detailed description of an embodiment of the latter which is illustrated by the following accompanying figures in which: FIG. Classic structure of a microbattery "all solid". Figure ibis: Classical structure of a microbattery with a protective layer between the electrolyte and the anode. Figures 2: Potential differences for cycles of charges and discharges of batteries with high internal resistance (a), with low internal resistance (b). Figure 3: Composition of LiP0-1 and LiP0-2 as a function of ionic conductivity, compared to the standard LiPON of the laboratory. Figure 4: Metal lnsulator Metal structure (M 1M) Figure Sa: Niyquist diagram of an MIM Ti / electrolyte / Ti (S = 0.1cm2). Experimental curve in gray and done in black. Figure 5b: equivalent circuit used for the fit Figure 6: Relative permitivity of electrolyte Li4P02,6 as a function of frequency. Figure 7: Cycling LiTiOS / LiPO / Si Li-ion battery between 1 and 3V.
    [0005] FIG. 8: Niyquist diagram of a battery with a two-layer electrolyte according to the invention FIG. 9: Cycling between 1 and 3V of a TiOS / LiPO / LiPON / Li battery.
    [0006] DETAILED DESCRIPTION OF PARTICULAR EMBODIMENTS Before beginning a detailed review of embodiments of the invention, are set forth below optional features that may optionally be used in combination or alternatively. It is recalled first of all that the invention relates to a solid electrolyte comprising a layer comprising LixPOy, free of nitrogen, with 3.6 x 6.3 and 1.5 y 4. Advantageously, x and y are such that the ionic conductivity is greater than or equal to 10-5 S / cm. Advantageously, the Li / O ratio of the layer comprising LixPOy is greater than 1, advantageously greater than or equal to 1.5.
    [0007] Advantageously, the layer comprising LixPOy comprises another element in an amount of less than 2.5%, advantageously less than 1%. Advantageously, the layer comprising LixPOy is exclusively a layer of LixPOy. Advantageously, the layer comprising LixPOy is such that x is equal to 4 and y is equal to 2.6. Advantageously, the layer comprising LixPOy is such that x is equal to 3.6 and y is equal to 2.3. Advantageously, the Li / P ratio is greater than or equal to 3.6. Advantageously, the ratio 0 / P is less than or equal to 4.
    [0008] Advantageously, the electrolyte is amorphous. Advantageously, the electrolyte comprises a protective layer of the layer comprising LixPOy. Advantageously, the protective layer has a minimum thickness of 0.5 nm and a maximum thickness of 35% of the thickness of the layer comprising LixPOy. Advantageously, the protective layer is a solid electrolyte. Advantageously, the protective layer is solid electrolyte chosen from LiPON or LizSiO. Advantageously, the electrolyte is a bi-layer preferentially LixPOy / LiPON 35 or LixPOy / LizSiO. Advantageously, the protective layer is chosen from A1203, Si, Li20.
    [0009] Another object of the invention is a microbattery comprising at least one solid electrolyte layer as described above. Advantageously, the microbattery comprises a layer of protection layer comprising Li, POy Advantageously, the protective layer has a minimum thickness of 0.5 nm and a maximum thickness of 35% of the thickness of the layer comprising LixPOy Advantageously, the protective layer is a solid electrolyte. Advantageously, the protective layer is a solid electrolyte chosen from LiPON or LizSiOw. Advantageously, the electrolyte is a bilayer preferentially LixPOy / LiPON or LixPOy / LizSiO, '. Advantageously, the protective layer is chosen from A1203, Si, Li20. Another object of the invention is a method of manufacturing an electrolyte as described above comprising a step of physical vapor deposition (PVD for Physical Vapor Deposition in English) from a target of Li 3 PO 4 sprayed under nitrogen to obtain a layer comprising LixPOy, nitrogen-free, with 3.6 x 6.3 and 1.5 y 4. Advantageously, the sputtering of the target is carried out without magnetron.
    [0010] A microbattery as illustrated in FIG. 1 and ibis is produced by the successive stacking of the following layers: a substrate 1 a current collector 2 a cathode material 3 an electrolyte material 4 possibly with a protective layer 6 anode material 5 - a current collector 2 The specificity of "all-solid" batteries is to have a solid electrolyte 4. The role of this electrolyte 4 is to ensure the transport of lithium ions from one electrode to the other battery while blocking the passage of electrons. The most commonly used embodiment for producing this electrolyte 4 is the sputtering of a target under vacuum. The principle of operation of a microbattery is based on the principle of oxido-reduction of lithium ions transiting between an anode material 5 and a cathode material 3 by the electrolyte 4. The electrons exchanged during these reactions pass through a external circuit thereby ensuring the charging or discharging of the battery.
    [0011] The contribution of lithium in the structure can be done either by the direct use of a layer of lithium metal as anode 5 in this case we speak of "lithium battery" or by the use of at least one material of electrode 4 lithiated in this case we speak of "Li-ion battery".
    [0012] According to the invention, a solid electrolyte 4 comprising a layer comprising Li, POy with 3.6x6.3 and 1.5y4. presents particularly interesting conductivity properties. The x and y values are molar values. These values are preferably determined by measuring chemical composition RBS (Rutherford Backscattering Spectrometry) and NRA (Nuclear Reaction Analysis).
    [0013] The layer comprising LixPO 4 according to the invention does not contain nitrogen. However, the ionic conductivity is very much higher than the ionic conductivity of the electrolytes of the state of the art. Preferably, the indices x and y are chosen so that the electrolyte has an ionic conductivity greater than or equal to 10-55 / cm. Advantageously, the electrical conductivity is for its part substantially identical. One of the characteristics of batteries is their internal resistance, it is she who will determine the behavior of the battery under strong currents of charge or discharge. This resistance is strongly dependent on the ionic conductivity of the electrolyte. With an electrolyte whose ionic conductivity is increased, it is possible to work at higher currents without losing capacity. The internal resistance is higher and the potential difference from the load regime to the discharge regime, or the opposite, is important, so the more the potential range actually cycled will be low. Potential differences are illustrated for charging cycles and discharges of high-resistance battery Figure 2a and low resistance Figure 2b. According to one possibility, the layer comprising LixPOy contains another element in an amount of less than 2.5%, advantageously less than 1 mol%. This element is for example boron. It may depend on the targets used for the manufacture of the electrolyte. This element is not nitrogen. In an alternative manner, the solid electrolyte according to the invention comprises a layer of LixPOyA, with A not being nitrogen and with 0 to 2.5. Preferably, the indices x and y are chosen so that the ratio Li / 0 is greater than 1, advantageously greater than or equal to 1.5. As a preferred example, the material is Li4PO2.6.
    [0014] The solid electrolyte according to the invention is amorphous.
    [0015] In FIG. 3, the ionic conductivity is indicated for three electrolytes: LiPON: electrolyte of the state of the art, LiPO.sub.1-1: Li.sub.3.6PO.sub.2.3, LiPO.sub.2-2: Li.sub.4 PO.sub.2.6. Li / P ratios; 0 / P and N / P are represented for each of the electrolytes. This figure shows a difference in particular ionic conductivity of the electrolytes according to the invention LiP0-1 and LiPO 2 compared to LiPON. We can also see an increase in the Li / P ratio while the other ratios remain substantially stable during the increase in ionic conductivity. It should be noted that, surprisingly, this electrolyte according to the invention also has good electrochemical stability.
    [0016] By way of example, the specific role, the chemical nature and the typical thicknesses of each layer of the microbattery are described below by way of example: the current collectors 2 are metallic and can be for example Pt-based , Cr, Au, Ti, VV, Mo, Ni. The thicknesses of these current collectors 2 are preferably between 100 nm and 1 μm, generally 250 nm. They serve to conduct the current homogeneously to the electrodes 3, 5. The cathode 3 or the positive electrode may consist of LiCoO 2, LiNiO 2, LiMn 2 O 4, CuS, CuS 2, VVOyS 2, TiO 2 S 2, LiTiS 2, Li 3 Ti 3 S, V 2 O 5. Depending on the materials chosen, thermal annealing may be necessary to increase the crystallization of the films and their insertion property. This is particularly the case for lithiated oxides. Nevertheless, certain amorphous materials, in particular titanium oxysulfides, do not require such treatment while allowing high insertion of lithium ions. The thickness of the cathode 3 is preferably between 100 nm and 10 pm. The cathode 3 is the place of the lithium reduction during the discharge of the microbattery and the oxidation thereof in charge The electrolyte 4 according to the invention is a good ionic conductor and electronic insulator. It is described above. The typical thickness is preferably 1.4 pm but it must be adjusted according to the thickness of the electrodes 3 and 5: it can vary between 500 nm and 3 pm. The anode 5 may be metal lithium deposited by thermal evaporation, a lithium-based metal alloy or an insertion compound (SiTON, SnNx, InNx, Si, Li4Ti5012, SnO2, etc.). There are also microbatteries without anode called Li free. In this case, a layer of lithium blocking metal is deposited. Lithium is then deposited on this layer. The thickness of the anode 5 is preferably between 100 nm and 10 pm. Anode 5 is the seat of the lithium oxidation during the discharge of the microbattery and the reduction during charging. According to one embodiment, the stack described above is encapsulated.
    [0017] The purpose of encapsulation is to protect the active stack from the external environment and specifically from moisture. Different strategies can be used: encapsulation from thin layers, encapsulation from co-laminates, or encapsulation by cowling, such as for example a glass cover maintained by parafilm.
    [0018] According to one embodiment of the invention, the microbattery comprises a protective layer 6 of the layer comprising LixPOy. This protective layer is intended to protect the interface between the layer comprising LixPOy and a metal. By way of example, this protective layer 6 is present between the layer comprising LixPOy and the anode 5 when the latter is metallic, such as titanium or lithium. This protective layer 6 prevents the formation of a strong interface resistance harmful to cycling the battery. The protective layer 6 reduces the internal resistance of the battery by keeping good electrode / electrolyte interfaces. Its thickness is preferably at least 0.5 nm and at most 35% of the thickness of the layer comprising LixPOy.
    [0019] According to this embodiment, the protective layer 6 may be a solid electrolyte. The solid electrolyte of the protective layer 6 is chosen from LiPON or LizSiOw. The protective layer 6 forms with LixPOy layer 4, an at least two-layer electrolyte comprising a layer comprising LixPOy and an electrolyte-type protective layer. The at least two-layer electrolyte is advantageously LixPOy / LiPON or LixPOy / LizSiOw. According to another possibility, the protective layer 6 may not be an ionic conductor such as, for example, Al 2 O 3, Si, Li 2 O or, more generally, materials of poor ionic conductivity, preferably the protective layer is deposited in a sufficiently fine manner to allow the passage of lithium ions.
    [0020] In another aspect, the invention relates to a method of manufacturing an electrolyte as described above. The method according to the invention comprises a step of depositing the layer comprising LixPOy in the vapor phase. This deposition is done for example from a target of the type Li3PO4 pulverized, advantageously without the use of a magnetron. Lithium, phosphorus and oxygen are brought by the target. According to one possibility, the spraying is carried out under nitrogen.
    [0021] Unlike the method of the state of the art nitrogen is not integrated in the layer comprising Li, P0y. This difference is due in particular to the absence of magnetron. Performing the sputtering without magnetron makes it possible to obtain a material that is very rich in lithium, in particular Li / P k 3 and relatively low in oxygen, in particular 0 / P 4. The Li / P ratio of the deposited electrolyte is greater than that of the target and the ratio 0 / P is lower than that of the target. The target can be consumed inhomogeneously. With the present invention the oxygen and lithium levels deposited are controlled in particular by the power, the pressure, the gas used preferentially set directly on the deposition device.
    [0022] According to one possibility, other gases may be used for spraying, for example: argon, oxygen, helium, xenon, neon, krypton or mixtures of these gases, such as, for example, a nitrogen mixture. argon, a nitrogen / oxygen mixture, an argon / nitrogen / oxygen mixture. Preferably, the flow rate of the gas or gas mixture is between 20 and 200 sccm.
    [0023] Advantageously, the pressure in the chamber is between 0.5 and 30 mTorr, preferably 4.5 mTorr. Preferably, the substrate 1, more generally referred to as the sample, is at floating potential. This arrangement makes it possible to obtain an electrolyte richer in lithium and thus having a better ionic conductivity.
    [0024] EXAMPLE 1 Deposition of an Electrolyte According to the Invention and Measurement of its Performance The thin layer electrolyte is deposited by PVD. The target used is Li 3 PO 4 and nitrogen sputtering is carried out without magnetron.
    [0025] The nitrogen flow rate is 100 sccm. The pressure in the chamber is 4.5 mTorr. The sample is at floating potential. The electrolyte is characterized by a structure MIM (Metal lnsulator Metal) titanium / electrolyte / titanium. This structure is illustrated in FIG. 4. A MIM structure is produced by the successive stacking of the following layers: a substrate 1 a current collector 2 an electrolyte material 3 possibly with a protective layer not shown a current collector The titanium of the current collector 2 is deposited by PVD, the deposited layers are localized by mechanical masking. The thickness of each current collector 2 is 250 nm and can vary between 250 nm and 500 nm. The thickness of the electrolyte 4 is 1400 nm and can vary between 500 nm and 2000 nm. In this case, the deposited electrolyte is a layer of Li4P02.6. This electrolyte is amorphous. Its ionic conductivity was measured by impedance spectroscopy between 1MHz and 1mHz with a deltaV of 10mV. The curve shown in Figure 5a is typical of an electrolyte. The value of the diameter of the semicircle makes it possible to calculate the ionic conductivity. The value of the semicircle is determined by mathematical regression by making a fit with the ECLab software from an equivalent circuit illustrated in FIG. 5b containing: a contact resistor R1 in series with a parallel circuit R2, C2 and in series with a capacity Ci, the ionic conductivity is 10-55 / cm. The electronic conductivity is 10-135 / cm. The permittivity is about 20E0 shown in Figure 6.
    [0026] Example 2 In this example, the Li4PO 2, 6 electrolyte is integrated in a LiTiOS / LiPO / Si type battery which cycles between 1 and 3V. The current collectors 2 are titanium, they are 250 nm thick and are deposited by PVD. The cathode 3 is TiO 2 deposited by reactive PVD of a titanium target under H25 and the thickness of the layer is 1.2 μm. 250 nm of lithium are deposited on the cathode 2 in TiOS by evaporation. They broadcast quickly through the TiOS. Electrolyte 4 LixPOy is deposited in the same way as in Example 1. The negative electrode, the anode 5 is made of silicon deposited by PVD of a silicon target under argon and is 10 nm thick. The battery is cycled between 1 and 3V at 1C. The results are shown in Figure 7. We see that the battery cycle correctly. Example 3 In this example, the Li4PO26 electrolyte is deposited as described above and a thin LiPON layer is deposited over it. This thin layer forms a protective layer of the electrolyte Li4P02 6. LiPON is deposited by PVD Radiofrequency magnetron with a target Li3PO4 (90% mol) - Li20 - B203. The thickness of the electrolyte Li 4 PO 2 6 can be 1.4 μm and that of LiPON from 100 to 500 nm. The electrolyte 4 is then formed by a LiPO / LiPON bi-layer. This application reduces the internal resistance of the battery by keeping good electrode / electrolyte interfaces. The resistance of the two-layer electrolyte (LiP0 + LiPON) is 40 Ohms (Figure 8). It was measured by impedance spectroscopy between 1MHz and 1mHz with a deltaV of 10mV. The resistance is given by the value of the 1/2 circle. The same thickness in LiPON would give a resistance of 120 Ohms. This bi-layer has a conductivity equivalent to 5.10-6S / cm. Example 4 In this example, the LiPO / LiPON electrolyte is integrated in a battery of the TiOS / LiPO / LiPON / Li type which cycles between 1 and 3V. The current collector 2 is titanium, it is 250 nm thick and is deposited by PVD. The cathode 3 is TiO 2 deposited by reactive PVD of a titanium target under H 2 S and the thickness of the layer is 1.2 μm. The LiP0 of the bi-layer electrolyte is deposited in the same manner as in Example 1 and is 1.4 μm and the LiPON of the bi-layer electrolyte is deposited as in Example 3 and is 250 nm. The anode 5 is made of lithium deposited by evaporation and is 2 pm thick. Lithium also serves as a current collector 2 on the side of the anode 5. The battery is cycled between 1 and 3V at 0.750. It can be seen in Figure 9 that polarization is very weak.15
    权利要求:
    Claims (13)
    [0001]
    REVENDICATIONS1. Solid electrolyte having a layer comprising Li, P0y, nitrogen-free, with 3.6 x 6.3 and 1.5 y 4.
    [0002]
    2. Electrolyte according to the preceding claim wherein x and y are such that the ionic conductivity is greater than or equal to 10-5 S / cm.
    [0003]
    An electrolyte according to any preceding claim wherein the Li / O ratio of the LixPOy layer is greater than 1 and preferably greater than or equal to 1.5.
    [0004]
    An electrolyte according to any one of the preceding claims wherein the layer comprising LixPOy comprises another element in an amount of less than 2.5% and preferably less than 1%.
    [0005]
    5. Solid electrolyte according to any one of claims 1 to 3 wherein the layer comprising LixPOy is exclusively a layer of LixPOy.
    [0006]
    An electrolyte according to any preceding claim wherein the layer comprising LixPOy is such that x is 4 and y is 2.6.
    [0007]
    An electrolyte according to any one of claims 1 to 5 wherein the layer comprising LixPOy is such that x is 3.6 and y is 2.3.
    [0008]
    Microbattery comprising at least one solid electrolyte layer according to any one of the preceding claims.
    [0009]
    9. Microbattery according to the preceding claim comprising a protective layer of the layer comprising LixPOy of a minimum thickness of 0.5 nm and a maximum thickness of 35% of the thickness of the layer comprising LixPOy.
    [0010]
    10. Microbattery according to the preceding claim wherein the protective layer is a solid electrolyte.
    [0011]
    11. Microbattery according to the preceding claim wherein the protective layer is a solid electrolyte selected from LiPON or LizSiOw.
    [0012]
    12. Microbattery according to claim 9 wherein the protective layer 6 is selected from A1203, Si, Li20.
    [0013]
    13. A method of manufacturing an electrolyte according to any one of claims 1 to 7 comprising a step of physically deposition in the vapor phase of an electrolyte layer from a target of Li3PO4 sprayed under nitrogen so as to obtain a layer comprising LixPOy, nitrogen-free, with 3.6 × 6.3 and 1.5 × 4.14. Manufacturing method according to claim 13 characterized in that the sputtering of the target is performed without magnetron.
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    同族专利:
    公开号 | 公开日
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    US9991555B2|2018-06-05|
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    引用文献:
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    FR2860925A1|2003-10-14|2005-04-15|Commissariat Energie Atomique|Microbattery includes a first electrode and electrolyte comprising a material with a tetrahedral structure with a central atom of phosphorus, boron, silicon, sulfur, molybdenum, vanadium or germanium|
    US8845764B2|2010-06-14|2014-09-30|Semiconductor Energy Laboratory Co., Ltd.|Power storage device comprising solid electrolyte layer over active material and second electrolyte and method of manufacturing the same|
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    CN110661033B|2018-06-28|2021-06-22|宁德时代新能源科技股份有限公司|Ion exchange material, preparation method thereof, electrolyte film and secondary battery|
    法律状态:
    2015-04-21| PLFP| Fee payment|Year of fee payment: 2 |
    2015-10-30| PLSC| Search report ready|Effective date: 20151030 |
    2016-04-26| PLFP| Fee payment|Year of fee payment: 3 |
    2017-04-27| PLFP| Fee payment|Year of fee payment: 4 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1453710A|FR3020503B1|2014-04-24|2014-04-24|SOLID ELECTROLYTE FOR MICRO BATTERY|FR1453710A| FR3020503B1|2014-04-24|2014-04-24|SOLID ELECTROLYTE FOR MICRO BATTERY|
    US14/695,577| US9991555B2|2014-04-24|2015-04-24|Solid electrolyte for a microbattery|
    EP15164957.1A| EP2937929B1|2014-04-24|2015-04-24|Solid electrolyte for micro-battery|
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