Solid-state battery and preparation method thereof

Abstract

The invention relates to a solid-state battery and a preparation method thereof. The solid state battery includes an electron and ion conductive membrane between an electrolyte membrane and an electrode membrane, where the electron and ion conductive membrane is formed as part of a current collector of the electrode and allows partial contact between the electrolyte and the electrode, the partial contact may be achieved by an ionically conductive material and optionally an electronically conductive material.

Description

Technical Field

[0001] The invention relates to a solid-state battery and a preparation method thereof. Background Art

[0002] Electronic components are present in a variety of portable devices, such as computers, mobile phones, tracking systems, optical readers, remote controls, etc. One of the disadvantages of these portable devices is the need to include a power supply. Portable devices generally use batteries as a power source. The battery must have sufficient capacity to power the device at least during the use period. Sufficient battery capacity means that the power pack is relatively bulky and / or large relative to the rest of the device. Therefore, it is desirable to have a smaller, lighter battery with sufficient energy storage capacity. Other energy storage devices, such as supercapacitors, and energy conversion devices, such as photovoltaic cells and fuel cells, are alternatives to batteries for power supply in portable electronic devices or non-portable appliances where appropriate. Another disadvantage of conventional batteries is that some batteries are made of potentially toxic materials that can leak and are subject to government regulations. Therefore, it is necessary to provide a safe source of electrical energy that can be charged / discharged multiple times.

[0003] In this context, a special type of energy storage device has been developed: solid-state batteries, especially thin-film batteries.

[0004] A solid-state battery, also known as a solid electrolyte battery or all-solid-state battery, refers to a storage device in which the electrolyte placed between the negative electrode and the positive electrode is solid, in the form of a glass plate, such as a glass plate made of lithium phosphate, or a gel.

[0005] This type of battery is seen as an alternative to lithium-ion batteries not only because solid-state batteries have a higher energy density, but also because they have a higher operating temperature range: from -20°C to over 100°C, compared to 15°C to 35°C, and a lower risk of flash fire or explosion. In a battery, cations move between the cathode and the anode via an ion conductor, transferring electrons to generate an electric current. In traditional batteries, such as lithium-ion batteries, the ion conductor is a highly flammable liquid organic compound, which is a major disadvantage.

[0006] In order to find high-performance solid conductors to replace liquid electrolytes, various research and development projects have led to the synthesis of various compounds. Researchers have discovered a solid ionic electrolyte that outperforms conventional lithium-ion electrolytes, namely solid sulfide electrolytes LGPS (LGPS: lithium, germanium, phosphorus, sulfur).

[0007] In the general context of battery electrodes, the available capacity, especially as a function of delivered power, is an important parameter for evaluating devices incorporating these electrodes, as is the speed at which the battery can be charged and discharged. It is well known and mentioned in the literature that increasing the discharge / charge current of a battery reduces the capacity that the battery can deliver (Coulombic efficiency).

[0008] Usually, in order to overcome these shortcomings, the active material can be mixed with a good electronic conductor (such as carbon), or the active material can be incorporated into a conductive matrix. In this case, the material of the positive electrode is embedded in the carbon matrix. EP3809491 is an example of this method. As shown in Figure 5, the carbon matrix reduces the capacitance loss at high current density.

[0009] The main limitation of this approach is the reduced overall capacity: a portion of the volume is used for the conductive matrix, which does not provide energy storage properties. The capacity will be reduced compared to a 100% active electrode. In addition, this approach is not easily applicable to solid-state thin-film batteries. Summary of the invention

[0010] It is therefore an object of the present invention to provide batteries, particularly thin film solid state batteries, which can reduce or even eliminate capacity loss during charge / discharge cycles.

[0011] Therefore, another object of the present invention is to make solid-state batteries, especially in LiCoO 2 It is possible to achieve these advantages, especially during the first charge, on thin-film batteries. BRIEF DESCRIPTION OF THE DRAWINGS

[0012] Figure 1 A cross-sectional view of a battery obtained according to an embodiment of the present application is shown.

[0013] Figure 2 A cross-sectional view of a battery obtained according to an embodiment of the present application is shown, wherein the negative electrode is shown.

[0014] Figure 3 A battery is shown whose electronically and ionically conductive membrane consists of or includes an electronically conductive material (metal grid, such as Pt) and an ionically conductive material (solid electrolyte, such as LiPON). Figure 3 A and C to H: Cross-sectional view of a cell in which the electron-conducting membrane is discontinuous. Figure 3 B: According to Figure 3 A is a top view of the membrane.

[0015] Figure 4A cross-sectional view of a battery according to the invention is shown, the battery comprising two stabilizing membranes, one between the positive electrode (positive electrode membrane) and the front current collector (electronic and ion conductive membrane forming part of the positive current collector), and the other between the front current collector and the electrolyte (electrolyte membrane). DETAILED DESCRIPTION

[0016] The present invention relates to a solid-state battery comprising an electronically and ionically conductive membrane separating an electrolyte membrane from a positive electrode membrane, the electronically and ionically conductive membrane constituting or forming part of an electrode current collector.

[0017] In particular, if Figure 1 As shown, the current collector of the electrode comprises a first current collector portion at the electrode-electrolyte interface, ie, the electron and ion conducting membrane, and a second current collector portion on one side of the electrode.

[0018] "Separating the electrolyte membrane from the electrode membrane" means in particular that the electronically and ionically conductive membrane is in contact with both the electrolyte membrane and the electrode membrane, the electrolyte membrane and the electrode membrane are not in contact with each other, or, in the case of a grid, especially a metal grid, the electrolyte and the electrode are in contact through holes in the grid.

[0019] The present invention also relates to a solid-state battery comprising an electronically and ionically conductive membrane between an electrolyte membrane and an electrode membrane, said electronically and ionically conductive membrane forming part of the electrode current collector and allowing partial contact between the electrolyte and the electrode, said partial contact possibly being achieved through an ionically conductive material and optionally an electronically conductive material.

[0020] For example, Figure 3 This is shown.

[0021] Any occurrence of "ionically conductive material" specifically refers to ionically conductive materials other than the electrolyte defined above.

[0022] In the absence of said ion conducting material, the electrolyte functions as the ion conducting material of the electron and ion conducting membrane.

[0023] "Partial contact" specifically refers to contact in at least one region of the electronic and ion membrane, which region does not represent the entire area of ​​the electronic and ion membrane.

[0024] In particular, the conductive film is discontinuous.

[0025] According to a specific embodiment, the contact area between the electrolyte and the electrode, especially the contact area with the positive electrode, is at least 10% of the total surface area of ​​the electrode, preferably between 20% and 75% of the total surface area of ​​the electrode.

[0026] The contacting is effected in particular at the level of at least one opening in the electron-conducting material of the electron- and ion-conducting membrane.

[0027] “At the level of at least one opening of the electron conducting material of the electron and ion conducting membrane” refers in particular to at least one opening in a thin film of electron conducting material, wherein the electron conducting material comprises the electrolyte and / or electrode as defined above.

[0028] According to a specific embodiment, the at least one opening comprises, in particular comprises only, the electrolyte, the positive electrode, or the electrolyte and the electrode as defined previously.

[0029] According to a specific embodiment, the at least one opening comprises, in particular only comprises, the previously defined electrolyte, or an electrolyte and an electrode. In this case, the electrolyte, in particular the electrolyte within the at least one opening, acts as an ion-conducting material for the electronically and ionically conductive membrane.

[0030] According to a specific embodiment, the at least one opening comprises, in particular comprises only, an electrode as defined above. In this case, the electrolyte, in particular the electrolyte in contact with the electrode, acts as the ion-conducting material of the electronically and ionically conducting membrane.

[0031] The present invention also relates to a solid-state battery comprising an electron-conducting membrane between an electrolyte membrane and an electrode membrane, the electron-conducting membrane forming part of the electrode current collector and allowing partial contact between the electrolyte and the electrode, the partial contact possibly being achieved by an ion-conducting material and optionally an electron-conducting material.

[0032] In this way, the electrolyte, particularly the electrolyte in contact with the electrode, and possibly the ion-conducting material, acts as an ion conductor.

[0033] More particularly, the electronic and ion conducting membrane consists of or comprises at least one electronic conducting material and at least one ion conducting material, the electronic conducting material comprising at least one opening, in particular a plurality of openings; the electronic and ion conducting membrane allows partial contact between the electrolyte and the electrode, the partial contact possibly being achieved via the ion conducting material and the optional electronic conducting material.

[0034] Even more particularly, the electronically and ionically conductive membrane consists of or comprises at least one electronically conductive material and at least one ionically conductive material, the electronically conductive material comprising at least one opening, in particular a plurality of openings; the electronically and ionically conductive membrane allows partial contact between the electrolyte and the electrode at the level of the at least one opening, the partial contact possibly being achieved via the ionically conductive material and the optional electronically conductive material.

[0035] Even more particularly, the electronically and ionically conducting membrane consists of or comprises at least one electronically conducting material and at least one ionically conducting material, the electronically conducting material comprising at least one opening, in particular a plurality of openings; the electronically and ionically conducting membrane allowing partial contact between electrolyte and electrode at the level of the at least one opening. In this case, the ionically conducting material is an electrolyte as defined above.

[0036] According to a specific embodiment, the present invention relates to a solid-state battery comprising an electronic and ion conductive membrane between an electrolyte membrane and a positive electrode membrane, wherein the electronic and ion conductive membrane forms part of the electrode current collector and allows partial contact between the electrolyte and the positive electrode, the ion conductive material and the optional electronic conductive material.

[0037] According to a specific embodiment, the present invention relates to a solid-state battery comprising an electronic and ion conductive membrane between an electrolyte membrane and an electrode membrane; the electronic and ion conductive membrane forms part of the electrode current collector and allows partial contact between the electrolyte and the positive electrode, the ion conductive material and the optional electronic conductive material.

[0038] According to a specific embodiment, the electronically and ionically conducting membrane comprises at least one electronically conducting material and optionally an ionically conducting material and at least one ionically conducting material and optionally an electronically conducting material.

[0039] According to a particular embodiment, the electron- and ion-conducting membrane comprises at least one electron-conducting material and optionally ions and at least one ion-conducting material.

[0040] According to a specific embodiment, the electronically and ionically conducting membrane comprises at least one electronically conducting material and at least one ionically conducting material.

[0041] According to a particular embodiment, the ion-conducting material is an electrolyte as defined above.

[0042] According to a specific embodiment, the electronically conductive material comprises at least one opening, in particular a plurality of openings.

[0043] According to a specific embodiment, the electronically conductive material comprises at least one opening in which the electrolyte is in contact with an electrode, in particular with a positive electrode, an ionically conductive material and optionally an electronically conductive material.

[0044] According to a specific embodiment, the electronically conductive material comprises at least one opening, in which the electrolyte is in contact with an electrode, in particular with a positive electrode, and the contact is achieved through the ionically conductive material.

[0045] The ion-conducting material is in particular an electrolyte as defined above. In this case, the invention more particularly relates to a solid-state battery comprising an electron- and ion-conducting membrane between an electrolyte membrane and an electrode membrane, the electron- and ion-conducting membrane forming part of an electrode current collector and comprising an electron-conducting material comprising at least one opening allowing partial contact between the electrolyte and the electrode.

[0046] In this case, it is the electrolyte that acts as an ion-conducting material that acts as an electron- and ion-conducting membrane.

[0047] In a specific embodiment, the present invention is directed to a solid-state battery comprising an electronically and ionically conductive membrane separating an electrolyte membrane from a cathode electrode membrane, the electronically and ionically conductive membrane forming part of a cathode current collector.

[0048] Figure 1 A battery according to the invention is shown.

[0049] According to a specific embodiment, the present invention relates to a battery, comprising:

[0050] a negative electrode current collector in contact with the electrolyte membrane; and

[0051] an electronically and ionically conductive membrane separating the electrolyte membrane from the positive electrode membrane;

[0052] Therein, the electronic and ion conductive membrane is formed as part of the positive electrode current collector.

[0053] According to a specific embodiment, the present invention relates to a battery, comprising:

[0054] A negative electrode current collector in contact with the negative electrode film;

[0055] an electrolyte membrane in contact with the negative electrode membrane; and

[0056] an electronically and ionically conductive membrane separating the electrolyte membrane from the positive electrode membrane;

[0057] Therein, the electronic and ion conductive membrane is formed as part of the positive electrode current collector.

[0058] "Separating the electrolyte membrane from the positive electrode membrane" specifically means that the electron and ion conducting membrane is in contact with both the electrolyte membrane and the positive electrode membrane, the electrolyte membrane and the positive electrode membrane are not in contact with each other, or, in the case of a grid, especially a metal grid, the electrolyte and the positive electrode are in contact through holes in the grid. As part of the positive current collector, the electron and ion conducting membrane can be attached to the positive pole of the battery.

[0059] In a specific embodiment, the present invention relates to a solid-state battery comprising an electronically and ionically conductive membrane separating an electrolyte membrane from a negative electrode membrane; the electronically and ionically conductive membrane forms part of a negative electrode current collector.

[0060] For example, the cathode electrode may be an intercalated cathode electrode.

[0061] As part of the negative current collector, the electronically and ionically conductive membrane may be attached to the negative pole of the battery.

[0062] The batteries in question are specifically all-solid-state batteries.

[0063] In particular, solid-state thin film batteries, especially all-solid-state thin film batteries, can also be referred to as solid-state thin film batteries, especially all-solid-state thin film batteries.

[0064] According to a specific embodiment, the thickness of the electronic and ion conducting membrane is from 10 nm to 1 μm.

[0065] According to a specific embodiment, the thickness E of the positive electrode film is 1 μm to 200 μm.

[0066] According to a specific embodiment, the thickness of the electron and ion conductive membrane is from 10 nm to E / 2, wherein E is the thickness of the positive electrode membrane as described above.

[0067] According to a specific embodiment, the present invention relates to a thin film battery, wherein:

[0068] The thickness of the negative electrode current collector is between 10 nm and 10 μm; and / or

[0069] The thickness of the negative electrode film is greater than 0 and less than or equal to 200 μm; and / or

[0070] The thickness of the electrolyte membrane is between 10 nm and 10 μm.

[0071] The thickness of the positive electrode film is between 1 μm and 200 μm.

[0072] The thickness of the electronic and ion conducting membranes is between 20nm and 1μm.

[0073] The "electron conductive membrane" means a membrane that allows electrons to be transferred from the electrolyte membrane to the positive electrode membrane and from the positive electrode membrane to the electrolyte membrane.

[0074] According to a specific embodiment, the electronic and ion conducting membrane has at least 10 -3 S.cm -1 For example, the conductivity can range from 10 -3 to 108 S.cm -1 .

[0075] By "ion-conducting membrane" is meant a membrane that allows ions, in particular lithium ions, to pass from the electrolyte membrane to the positive electrode membrane and vice versa.

[0076] According to a specific embodiment, the electronic and ion conducting membrane has at least 10 -6 S.cm -1 For example, the ionic conductivity can be 10 -8 to 10 -2 S.cm -1 between.

[0077] According to a specific embodiment, the electron- and ion-conducting membrane is made of or comprises at least one electron- and ion-conducting material.

[0078] According to a specific embodiment, the electronic and ion conducting membrane consists of or comprises a material M, wherein the material M is selected from:

[0079] Optionally doped metals and their alloys, the metal being in particular selected from Si, Sn, Al, As;

[0080] Carbon-based materials, in particular carbon-based materials selected from mesocarbon microbeads (MCMB), highly ordered pyrolytic graphite (HOPG), hard carbon and soft carbon;

[0081] LiTiO 2 (corresponding to TiO after lithium insertion 2 status); and / or

[0082] LiFePO 4 .

[0083] The metal may be doped with B, As or P. The content of the dopant in the metal or its alloy is <1%.

[0084] According to a specific embodiment, the electronic and ion conductive membrane contains 95% to 100% by weight of material M, more specifically, 100% by weight of material M. "Mass ratio" refers to the percentage of the mass of material M to the total mass of the electronic and ion conductive membrane.

[0085] According to a specific embodiment, the electronic and ion-conducting membrane is made of at least one electronically conductive material and at least one ion-conducting material, or comprises at least one electronically conductive material and at least one ion-conducting material. A battery according to the invention comprising such a membrane is Figure 2 shown.

[0086] According to a more specific embodiment, the electronically and ionically conducting membrane is made of or comprises an electronically conducting material and an ionically conducting material.

[0087] The electron conducting material is particularly present in the form of a grid.

[0088] "Grid" refers specifically to a perforated layer or plate, or an assembly of interlaced or parallel wires or rods.

[0089] The (at least one) electronically conductive material may be selected from:

[0090] The metal, for example Pt, W, Al, Cu, Au or Ti, is present in particular in the form of a grid.

[0091] The ion-conducting material is, in particular, an electrolyte, in particular a solid electrolyte. These electrolytes are well known in the literature.

[0092] The (at least one) ion-conducting material may be selected from:

[0093] Solid electrolytes, especially LiPON (lithium phosphorus oxynitride), LLTO (lithium lanthanum titanate), LLZO (Li 7 La 3 Zr 2 O 12 ), LPS (lithium phosphide), LTP (lithium titanium phosphate), LZP (lithium zirconium phosphate), LiSiON (lithium silicon oxynitride), LAGP (lithium aluminum germanium phosphate), LGPS (lithium germanium phosphosulfide), and optionally a PEO (polyethylene oxide)-based solid electrolyte, in particular a solid electrolyte constituting or contained in the electrolyte membrane of the battery of the present invention.

[0094] The properties of the negative electrode current collector, the negative electrode film, the electrolyte membrane and the negative electrode film are well known to those skilled in the art and can be easily determined by those skilled in the art.

[0095] For example:

[0096] The negative electrode current collector is made of or includes a material selected from Si-doped Ti, Pt, Cu, Al, Au, W, TiN, such as Ti;

[0097] The negative electrode film is selected from Li, Al, C, In 2 O 3 、Si、SnO 2 、TiO 2 or V 2 O 5, such as Li or a material selected from Li, Al, C, In 2 O 3 、Si、SnO 2 、TiO 2 or V 2 O 5 , such as Li materials;

[0098] The electrolyte membrane consists of or includes a material selected from LiPON, LLTO, LLZO, LPS, LTP, LZP, LiSiON, LiN, LAGP, LGPS, a PEO-based material, such as LiPON; and / or

[0099] The positive electrode film is made of LiCoO 2 、LiFePO 4 、LiMn 2 O 4 、LiNiO 2 ,LiV 3 O 8 、LiMoO 3 ,LiV 2 O 5 , NMC, such as LiCoO 2 The material composition or includes LiCoO 2 、LiFePO 4 、LiMn 2 O 4 、LiNiO 2 ,LiV 3 O 8 、LiMoO 3 ,LiV 2 O 5 , NMC, such as LiCoO 2 For example, methods for producing such electrode films are described in the papers of Liu et al. (Advanced Materials, vol. 26, no. 37, pp. 6472-6477, 2014), Tadanaga et al. (Materials Research Bulletin, vol. 53, pp. 196-198, 2014), and Liu et al. (Electrochimica Acta, vol. 56, no. 3, pp. 1392-1398, 2011).

[0100] According to one particular embodiment, the negative electrode and / or the positive electrode of the battery of the invention is a material of the AAM type (“all-active material”).

[0101] "AAM type" specifically means that the electrode does not contain inactive additives.

[0102] “Free” refers specifically to electrodes, especially electrodes for thin-film batteries, containing less than 5% by mass, or even less than 1% by mass of inactive additives based on the total mass of the electrode.

[0103] According to a specific embodiment, the positive electrode film is also in contact with the substrate.

[0104] The nature of the substrate is well known in the art and can be readily determined by one skilled in the art.

[0105] The substrate is made of Siv 2 Or made of Si material or containing SiO 2 Or Si material.

[0106] According to a more specific embodiment, said substrate is electrically conductive.

[0107] In a specific embodiment, the solid-state battery further comprises a current collector between the substrate and the electrode. In this case, this element is also formed as part of the current collector of the electrode as is the electron- and ion-conducting membrane.

[0108] According to a specific embodiment, the negative electrode current collector film is also in contact with the passivation film.

[0109] The properties of passivation films are well known in the art and can be readily determined by one skilled in the art.

[0110] For example, the passivation film consists of or includes a polyparaxylene (PPX) material.

[0111] According to a more specific embodiment, the negative electrode current collector film is additionally in contact with a passivation film, and the negative electrode current collector film and the passivation film are also in contact with a redistribution film (also referred to as a contact recovery film or RDL).

[0112] The redistribution film is made of, for example, a titanium material or includes the material.

[0113] Therefore, the battery according to the present invention comprises a stack in the following order:

[0114] Positive electrode film;

[0115] an electronically and ionically conductive membrane formed as part of the positive electrode current collector;

[0116] an electrolyte membrane; and

[0117] Anode current collector;

[0118] Or stacked in the following order:

[0119] Positive electrode film;

[0120] an electronically and ionically conductive membrane formed as part of the positive electrode current collector;

[0121] Electrolyte membrane;

[0122] A cathode electrode film; and

[0123] Anode current collector;

[0124] Or stacked in the following order:

[0125] substrate;

[0126] Positive electrode film;

[0127] an electronically and ionically conductive membrane formed as part of the positive electrode current collector;

[0128] Electrolyte membrane;

[0129] a cathode electrode film; and

[0130] Anode current collector;

[0131] Or stacked in the following order:

[0132] substrate;

[0133] Positive electrode film;

[0134] an electronically and ionically conductive membrane formed as part of the positive electrode current collector;

[0135] Electrolyte membrane;

[0136] Negative electrode film;

[0137] a negative electrode current collector; and

[0138] Passivation film and redistribution film.

[0139] Other membranes may be inserted between the positive electrode (positive electrode membrane) and the front current collector (electronic and ion conducting membrane forming part of the positive current collector), and / or between the front current collector and the electrolyte (electrolyte membrane). Such membranes are e.g. Figure 3 shown.

[0140] These membranes are likely to help improve both chemical properties (preventing chemical degradation) and physical properties (improving adhesion and uniformity of lithium flow).

[0141] Examples of such membranes include:

[0142] C.In 2 O 3, Li 1.2 Mn 0.6 Ni 02 O 2 、Al 2 O 3 、ZrO 2 、AlPO 4 , as described in the papers Lyu et al, Advanced Energy Materials, vol.11, n 2, p.2000982, 2021 and G Hu, J. Cao, Z. Peng, Y Cao, et K. Du, Electrochimica Acta, vol.149, p.49-55, Dec.2014.

[0143] Contains Li 4 Ti 5 O 12 , Li 2 TiO 3 、TiO 2 LiCoO in powder form 2 coating, as described in the paper Z. Li et al, J. Power Sources, vol. 541, p. 231703, sept. 2022.

[0144] LTO, LLZO, LiTaO 3 、LiAlO 2 、LiNbO 3 , NASICON, etc., as described in the paper A. Banerjee et al., Chem. Rev. vol. 120, n 14, p. 6878-6933, July 2020.

[0145] The thickness of these films ranges from 1 nm to 50 nm.

[0146] According to another aspect, the invention also relates to a method for preparing a battery as defined above, comprising the step of depositing an electronically and ionically conductive membrane on a positive electrode membrane.

[0147] The deposition can be carried out using techniques well known to the skilled person, in particular thin film deposition techniques, for example,

[0148] Through atomic layer etching (ALE),

[0149] Through atomic thin layer deposition or ALD,

[0150] Thin films are deposited by evaporation.

[0151] Thin films are deposited by sputtering.

[0152] by electrodeposition of thin films.

[0153] The other elements of the battery can be installed using one of the techniques familiar to a person skilled in the art, for example as described in A Kozen et al., Chem. Mater. 2015, 27, 15, 5324-5331; EMF Vieira et al, EMF Vieira et al., J. Phys. D.: Appl. Phys, 2016, 49, 48, 5301 (WO 2008019398A1).

[0154] According to another aspect, the invention also relates to the use of a battery according to the invention as a solid-state battery, in particular as an integrated solid-state microbattery, for powering an electrical device, in particular a portable device.

[0155] For example, the device is a (bio)medical device, in particular an implantable (bio)medical device, or an electronic entertainment device, in particular an augmented reality device.

[0156] definition

[0157] As understood herein, a range of values ​​of the form "xy" or "from x to y" or "between x and y" includes the x and y endpoints, as well as the integers between those endpoints. For example, "1-5" or "from 1 to 5" or "between 1 to 5" specifically refers to the integers 1, 2, 3, 4, and 5. Preferred embodiments include each individual integer within the range of values, as well as any subcombination of those integers. For example, preferred values ​​for "1-5" may include the integers 1, 2, 3, 4, 5, 1-2, 1-3, 1-4, 1-5, 2-3, 2-4, 2-5, etc.

[0158] As used in this description, the term "about" refers to a value within the range of ±10% of a particular value. For example, the term "about 20" includes values ​​of 20±10%, ie, values ​​of 18 to 22.

[0159] For the purpose of this description, unless otherwise stated, percentages refer to mass percentages relative to the total mass of the formulation.

[0160] A film may be understood in particular to be a stratum of superimposed or stacked elements.

[0161] Example

[0162] A method for preparing a thin film solid-state battery according to the present invention is as follows.

[0163] ALD was used to deposit 20 μm thick LiCoO 2 A 100 nm thick amorphous TiO2 layer was deposited on the positive electrode film. 2Then add the LIPON electrolyte membrane (thickness 1μμm) and the Ti negative electrode collector to obtain the active part of the battery.

[0164] Other battery components (support material: SiO 2 , passivation film: PPX, contact recovery film: Ti), are arranged in a manner familiar to technicians.

[0165] At 1mA.cm -2 Under the condition of -2 , i.e., an increase of +50% compared to the prior art (the current collector is placed under the positive electrode membrane and also in contact with the electrolyte membrane).

[0166] In addition, the capacitance retention rate is more stable from 0.1 to 10mA.cm -2 The loss is only 10% compared to 30% for the existing technology.

[0167] Figure 1 An example of a battery produced in this way is shown.

Claims

1. A solid-state battery comprising an electronic and ion conducting membrane between an electrolyte membrane and an electrode membrane, wherein: The electronically and ionically conductive membrane forms part of the current collector of the electrode and allows partial contact between the electrolyte and the electrode, possibly via an ionically and optionally an electronically conductive material.

2. The battery according to claim 1, wherein The battery comprises: a negative electrode current collector in contact with the electrolyte membrane; and an electronically and ionically conductive membrane separating the electrolyte membrane from the positive electrode membrane; Therein, the electron and ion conductive membrane is formed as part of the positive electrode current collector.

3. The battery according to claim 1, wherein The battery comprises: A negative electrode current collector in contact with the negative electrode film; an electrolyte membrane in contact with the negative electrode membrane; and an electronically and ionically conductive membrane separating the electrolyte membrane from the positive electrode membrane; Therein, the electron and ion conductive membrane is formed as part of the positive electrode current collector.

4. A battery according to any one of the preceding claims, wherein The thickness of the electron and ion conducting membrane is from 10 nm to 1 μm.

5. A battery according to any one of the preceding claims, wherein The thickness E of the positive electrode film is 1 μm to 200 μm.

6. A battery according to any one of the preceding claims, wherein The thickness of the electron and ion conductive membrane is 10 nm to E / 2, wherein E is the thickness of the positive electrode membrane described in claim 5.

7. A battery according to any one of the preceding claims, wherein The electronic and ion conducting membrane comprises an electronic and ion conducting material selected from the following options: An optionally doped metal selected from Si, Sn, Al, As and alloys thereof; Carbon-based materials selected from mesocarbon microbeads (MCMB), highly ordered pyrolytic graphite (HOPG), hard carbon and soft carbon; LiTiO2; and / or LiFePO4.

8. The battery according to any one of claims 1 to 6, wherein the electronically and ionically conductive membrane comprises at least one electronically conductive material and at least one ionically conductive material, The at least one electronically conductive material is selected from the group consisting of metals Pt, W, Al, Cu, Au and Ti, in particular, the metal is present in the form of a grid, and / or The at least one ion-conducting material is selected from the group consisting of solid electrolytes LiPON, LLTO, LLZO, LPS, LTP, LZP, LiSiON, LAGP, LGPS and optionally PEO-based solid electrolytes, And the solid electrolyte constitutes or is contained in the electrolyte membrane defined in claim 1.

9. A method of preparing a battery according to any one of claims 1 to 8, said method comprising the step of depositing said electronic and ion conducting membrane on said positive electrode membrane.

10. The method according to claim 9, wherein: The deposition step is performed by atomic layer etching.

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