Solid electrolyte membrane, electrolyte electrode sheet, solid-state battery, preparation method and electric device

Abstract

Disclosed are a solid electrolyte membrane, an electrolyte electrode sheet, a solid-state battery, a preparation method and an electric device. The solid electrolyte membrane comprises a first electrolyte layer, wherein the first electrolyte layer comprises a sulfide solid electrolyte and a first layer of binders, and the first layer of binders comprises a first binder having a relatively low water absorption rate. The electrolyte electrode sheet comprises an electrode body and a solid electrolyte membrane located on at least one side of the electrode body, or comprises an electrode body and a first electrolyte layer located on at least one side of the electrode body. The solid-state battery comprises at least one of a first electrolyte layer, a solid electrolyte membrane and an electrolyte electrode sheet.

Description

Solid electrolyte membrane, electrolyte electrode, solid-state battery, preparation method and electrical device

[0001] Related applications

[0002] This application claims priority to Chinese patent application filed on November 8, 2024, with application number CN2024115955786, entitled "Solid electrolyte membrane, electrolyte electrode, solid battery, preparation method and electrical device", the entire contents of which are incorporated herein by reference. Technical Field

[0003] This application relates to the field of solid-state battery technology, and further to solid electrolyte membranes, electrolyte electrodes, solid-state batteries, preparation methods and electrical devices thereof, and even further to solid electrolyte membranes and their preparation methods, electrolyte electrodes, solid-state batteries and their preparation methods and electrical devices thereof. Background Technology

[0004] The statements herein are provided only as background information in connection with this application and do not necessarily constitute prior art.

[0005] Solid-state batteries utilize non-flammable solid electrolytes to replace the organic electrolytes in traditional liquid secondary batteries, significantly improving battery safety. Among numerous solid electrolyte materials, sulfide solid electrolytes, with their ultra-high ionic conductivity and excellent mechanical properties, have become one of the most promising solid electrolyte materials for practical application and industrialization. However, the chemical stability in aqueous atmospheres is one of the most serious problems facing sulfide solid electrolytes. Water in the air reacts with sulfides to produce highly toxic and harmful hydrogen sulfide gas, further accelerating the degradation of sulfides and severely restricting the practical application of sulfide solid electrolytes. Summary of the Invention

[0006] In view of the above problems, according to various embodiments and examples of this application, this application provides a solid electrolyte membrane, an electrolyte electrode, a solid-state battery, a preparation method, and an electrical device, and further provides a solid electrolyte membrane and its preparation method, an electrolyte electrode, a solid-state battery and its preparation method, and an electrical device. The hydrogen sulfide release from this solid electrolyte membrane, electrolyte electrode, and solid-state battery in an aqueous environment is significantly reduced.

[0007] In some embodiments of the first aspect of this application, a solid electrolyte membrane is provided, which includes a first electrolyte layer, the first electrolyte layer including a sulfide solid electrolyte and a first adhesive layer, the first adhesive layer including a first adhesive.

[0008] The first adhesive satisfies one or more of the following characteristics:

[0009] (t1) The water absorption rate of the first adhesive is ≤0.1%;

[0010] (t2) The first binder comprises a cyclic olefin / chain olefin copolymer, wherein the monomer units of the cyclic olefin / chain olefin copolymer include cyclic olefin monomer units and chain olefin monomer units, and the chain backbone of the cyclic olefin / chain olefin copolymer includes a cyclic structure provided by the cyclic olefin monomer units.

[0011] In some embodiments, a solid electrolyte membrane is provided, which includes a first electrolyte layer, the first electrolyte layer including a first solid electrolyte and a first binder layer;

[0012] Wherein, the first solid electrolyte includes a sulfide solid electrolyte; the first layer binder includes a first binder, wherein the water absorption rate of the first binder is less than or equal to 0.1%.

[0013] In some embodiments, the first binder comprises a cyclic olefin / chain olefin copolymer, wherein the monomer units of the cyclic olefin / chain olefin copolymer include cyclic olefin monomer units and chain olefin monomer units, and the chain backbone of the cyclic olefin / chain olefin copolymer includes a cyclic structure provided by the cyclic olefin monomer units.

[0014] In some embodiments, a solid electrolyte membrane is provided, comprising a first electrolyte layer, the first electrolyte layer comprising a sulfide solid electrolyte and a first binder layer, the first binder layer comprising a first adhesive.

[0015] The first binder comprises a cyclic olefin / chain olefin copolymer, wherein the monomer units of the cyclic olefin / chain olefin copolymer include cyclic olefin monomer units and chain olefin monomer units, and the chain backbone of the cyclic olefin / chain olefin copolymer includes a cyclic structure provided by the cyclic olefin monomer units.

[0016] The first binder is a binder with low water absorption, which may have a water absorption rate of ≤0.1%. The first binder may include cyclic olefin / chain olefin copolymers with low water absorption, for example, cyclic olefin / chain olefin copolymers with a water absorption rate of ≤0.01%.

[0017] By introducing a first binder with low water absorption rate into the solid electrolyte membrane containing a sulfide solid electrolyte, the absorption of water by the solid electrolyte membrane can be reduced, the probability of contact reaction between the sulfide solid electrolyte and water can be decreased, and the decomposition of the sulfide solid electrolyte can be reduced or inhibited, thus significantly reducing the amount of hydrogen sulfide released by the solid electrolyte membrane in an aqueous environment (such as air). Furthermore, the amount of hydrogen sulfide released by the electrolyte electrode and solid-state battery prepared based on this solid electrolyte membrane in an aqueous environment (such as air) can be correspondingly reduced.

[0018] On the other hand, as the probability of contact reaction between sulfide solid electrolyte and water decreases, the material stability of sulfide solid electrolyte can be improved, which is conducive to giving full play to the fast ion conduction characteristics of sulfide solid electrolyte and maintaining good ionic conductivity of solid electrolyte membrane.

[0019] On the other hand, as the probability of contact reaction between sulfide solid electrolyte and water decreases, the stability of related materials in electrolyte electrodes and solid-state batteries, including the solid electrolyte membrane, is also improved, which can improve the electrochemical performance stability of solid-state batteries.

[0020] On the other hand, when using a solid electrolyte membrane to prepare a solid-state battery, it may be difficult to avoid contact with moisture in the air during operation. When using the aforementioned solid electrolyte membrane, which includes a first electrolyte layer, to prepare a solid-state battery, the probability of degradation of sulfide solid electrolyte during operation can be reduced, the air stability of the solid electrolyte membrane, electrolyte electrode and solid-state battery can be improved, and the quality stability of the solid-state battery can be improved.

[0021] The improvement described in any part of the context of this application is not intended to be limited to any theory.

[0022] In some embodiments, the first adhesive satisfies one or more of the following characteristics:

[0023] The chain backbone of the cyclic olefin / chain olefin copolymer is a carbon backbone;

[0024] The cyclic olefin / chain olefin copolymer is an aliphatic polymer;

[0025] The cyclic structure in the cyclic olefin monomer unit includes one or more of monocyclic and polycyclic structures;

[0026] The number of ring atoms in the cyclic olefin monomer unit is 3 to 30, and can be selected as 5 to 20;

[0027] The olefin monomer unit includes those corresponding to C. 2～6 The structural unit of olefins;

[0028] The side groups of the cyclic olefin / chain olefin copolymer include C 1～20 Aliphatic chains and fluorinated C 1～20 One or more of the aliphatic chains;

[0029] In the cyclic olefin / chain olefin copolymer, the molar fraction of the cyclic olefin monomer unit is 10% to 85%, and can be selected as 50% to 85%;

[0030] In the cyclic olefin / chain olefin copolymer, the molar fraction of the chain olefin monomer unit is 15% to 70%, and can be selected as 15% to 50%.

[0031] The weight-average molecular weight of the cyclic olefin / chain olefin copolymer is 30kDa to 100kDa, and can be selected as 30kDa to 50kDa.

[0032] In some embodiments, the first adhesive satisfies one or more of the following characteristics:

[0033] The number of ring atoms in the cyclic olefin monomer unit is 5 to 20;

[0034] The cyclic olefin monomer units include structural units corresponding to one or more monomers selected from norbornene, cyclopentene, cycloheptene, cyclohexene, and cycloheptene;

[0035] The chain olefin monomer unit includes a structural unit corresponding to ethylene;

[0036] The side groups of the cyclic olefin / chain olefin copolymer include C 1～10 Alkyl chains and fluorinated C 1～10 One or more of the alkyl chain;

[0037] In the cyclic olefin / chain olefin copolymer, the molar fraction of the cyclic olefin monomer unit is 30% to 85%;

[0038] In the cyclic olefin / chain olefin copolymer, the molar fraction of the chain olefin monomer unit is 15% to 50%;

[0039] The weight-average molecular weight of the cyclic olefin / chain olefin copolymer is 30 kDa to 50 kDa.

[0040] When the cyclic olefin / chain olefin copolymer is an aliphatic reactant, the molecule does not contain an aromatic ring, which is beneficial for the cyclic olefin / chain olefin copolymer to have a more suitable dielectric constant. When preparing slurries containing non-polar or low-polar solvents, it is beneficial for improving the dispersion uniformity of the slurry system.

[0041] By adjusting one or more parameters, such as the type and size of the rings in the cyclic olefin monomer unit, the number of carbon atoms in the chain olefin monomer unit, the molar fraction of the cyclic olefin monomer unit, the mass fraction of the cyclic olefin monomer unit, the molar fraction of the chain olefin monomer unit, the mass fraction of the chain olefin monomer unit, and the weight-average molecular weight of the cyclic olefin / chain olefin copolymer, one or more of the following can be adjusted: the flexibility or rigidity of the cyclic olefin / chain olefin copolymer, the viscosity of the electrolyte slurry, and the dispersing effect on sulfide solid electrolytes. As a non-limiting example, increasing the content of cyclic olefin monomer units can increase molecular rigidity, increasing the content of chain olefin monomer units can increase molecular flexibility, increasing the weight-average molecular weight can increase the viscosity of the electrolyte slurry, and adjusting the adhesion and dielectric constant can regulate the dispersing effect on sulfide solid electrolytes.

[0042] On another front, the water absorption characteristics of cyclic olefin / chain olefin copolymers can be adjusted by regulating the ratio between cyclic olefin monomer units and chain olefin monomer units. A higher proportion of cyclic olefin monomer units is more conducive to reducing water absorption. In addition, processing performance can also be taken into account.

[0043] When the side groups of the cyclic olefin / chain olefin copolymer include fluorinated groups (such as fluorinated aliphatic chains, or even fluorinated alkyl chains), it is beneficial to improve the fluidity of the slurry and further improve the dispersion uniformity of the slurry.

[0044] By adjusting one or more of the aforementioned parameters within the aforementioned range, it is more beneficial to improve at least one of the following items: low water absorption of cyclic olefin / chain olefin copolymers, material stability of sulfide solid electrolytes, dispersion stability of electrolyte slurry, coating uniformity of electrolyte slurry, and dispersion uniformity of electrolyte slurry.

[0045] In some embodiments, the cyclic olefin / chain olefin copolymer includes one or more of (ethylene-cyclopentene) copolymers, (ethylene-norbornene) random copolymers, and (ethylene-norbornene) alternating copolymers.

[0046] The aforementioned types of cyclic olefin / chain olefin copolymers can better control at least one of the following: the low water absorption characteristics of cyclic olefin / chain olefin copolymers, the material stability of sulfide solid electrolytes, the dispersion stability of electrolyte slurries, the coating uniformity of electrolyte slurries, and the dispersion uniformity of electrolyte slurries.

[0047] In some embodiments, the water absorption rate of the first adhesive is less than or equal to 0.05%; optionally, the water absorption rate of the first adhesive is less than or equal to 0.02%; further optionally, the water absorption rate of the first adhesive is less than or equal to 0.01%.

[0048] By controlling the water absorption rate of the first binder within the aforementioned range, the water absorption of the solid electrolyte membrane can be further reduced, which is more conducive to reducing or inhibiting the decomposition of sulfide solid electrolytes and can better reduce the release of hydrogen sulfide from solid electrolyte membranes, electrolyte electrodes and solid batteries in water-containing environments (such as air).

[0049] On the other hand, by controlling the water absorption rate of the first binder within the aforementioned range, it is more conducive to suppressing the decomposition of sulfides, more conducive to improving the material stability of sulfide solid electrolytes, and more conducive to maintaining good ionic conductivity of the solid electrolyte membrane; furthermore, it is more conducive to improving the electrochemical performance stability of solid-state batteries.

[0050] On the other hand, by controlling the water absorption rate of the first binder within the aforementioned range, it is more beneficial to reduce the degradation probability of the sulfide solid electrolyte during the preparation of solid-state batteries using a solid electrolyte membrane including the first electrolyte layer. This is beneficial to further improve the air stability of the solid electrolyte membrane, electrolyte electrode and solid-state battery, and can improve the quality stability of solid-state batteries.

[0051] In some embodiments, the first electrolyte layer satisfies one or more of the following characteristics:

[0052] The first adhesive accounts for 15% to 100% of the weight of the first layer of adhesive, optionally 40% to 95%, and more preferably 50% to 75%.

[0053] The first adhesive has a weight percentage of 0.3% to 6% in the first electrolyte layer, optionally 0.3% to 4%, and more preferably 0.5% to 2%;

[0054] The sulfide solid electrolyte has a weight percentage of 94% to 99.5% in the first electrolyte layer, and can be optionally 95% to 98%.

[0055] In some embodiments, the first electrolyte layer satisfies one or more of the following characteristics:

[0056] The weight percentage of the first adhesive in the first layer of adhesive is 50% to 75%;

[0057] The first adhesive comprises 0.5% to 2% by weight in the first electrolyte layer;

[0058] The sulfide solid electrolyte accounts for 95% to 98% of the weight of the first electrolyte layer.

[0059] By controlling one or more parameters among the following within the aforementioned ranges—the weight percentage of the first binder in the first layer of binder, the weight percentage of the first binder in the first electrolyte layer, and the weight percentage of the sulfide solid electrolyte in the first electrolyte layer—it is advantageous to reduce hydrogen sulfide release, improve the material stability of the sulfide solid electrolyte, and also enable the solid electrolyte membrane to have higher ionic conductivity.

[0060] In some embodiments, the first electrolyte layer further includes a second binder, the second binder having a water absorption rate greater than or equal to 0.5%, optionally greater than or equal to 1%, and further optionally greater than or equal to 2%.

[0061] In some embodiments, the second adhesive includes one or more of nitrile rubber, styrene-butadiene rubber, hydrogenated nitrile rubber, natural rubber, etherified cellulose, polymethyl methacrylate, polyethylene oxide methyl vinyl silicone rubber, and derivatives of any of the foregoing; wherein the water absorption rate of the derivative is ≥0.5%;

[0062] Optionally, the second adhesive includes at least one of nitrile rubber and nitrile rubber derivatives, wherein the nitrile rubber derivatives include hydrogenated nitrile rubber.

[0063] By incorporating the aforementioned type of second binder into the first electrolyte layer, it is beneficial to reduce hydrogen sulfide release and improve the material stability of the sulfide solid electrolyte. Simultaneously, it allows for better control of the dispersion uniformity, dispersion stability, and coating uniformity of the slurry system in the first electrolyte layer. This, in turn, improves the component distribution uniformity of the first electrolyte layer and the uniformity and stability of the electrical contact network. From this perspective, it is beneficial to improve the electrochemical performance of solid-state batteries, such as, but not limited to, improving their cycle performance. Furthermore, utilizing the excellent low water absorption characteristics provided by the first binder can significantly reduce the water absorption problems that are easily caused by introducing the second binder, greatly suppressing the battery performance degradation that may result from water absorption by the first binder. The synergistic effect between the first and second binders can further improve the component dispersion uniformity and material stability of the solid electrolyte membrane, allowing the second binder to better enhance the electrochemical performance of the solid-state battery.

[0064] In some embodiments, the first electrolyte layer satisfies one or more of the following characteristics:

[0065] The second adhesive accounts for 0% to 85% of the weight of the first adhesive layer, optionally 5% to 60%, and more preferably 25% to 50%.

[0066] The sum of the weight percentages of the first adhesive and the second adhesive in the first electrolyte layer is 0.5% to 6%, optionally 2% to 5%;

[0067] The weight percentage of the first adhesive in the sum of the weights of the first adhesive and the second adhesive is 15% to 100%, optionally 40% to 95%, and further optionally 50% to 75%;

[0068] The weight percentage of the second adhesive in the sum of the weights of the first adhesive and the second adhesive is 0% to 85%, optionally 5% to 60%, and further optionally 25% to 50%.

[0069] In some embodiments, the first electrolyte layer satisfies one or more of the following characteristics:

[0070] The first adhesive accounts for 15% to 100% of the weight of the first layer of adhesive, optionally 40% to 95%, and more preferably 50% to 75%.

[0071] The second adhesive accounts for 0% to 85% of the weight of the first adhesive layer, optionally 5% to 60%, and more preferably 25% to 50%.

[0072] The first adhesive has a weight percentage of 0.3% to 6% in the first electrolyte layer, optionally 0.3% to 4%, and more preferably 0.5% to 2%;

[0073] The sum of the weight percentages of the first adhesive and the second adhesive in the first electrolyte layer is 0.5% to 6%, optionally 2% to 5%;

[0074] The sulfide solid electrolyte has a weight percentage of 94% to 99.5% in the first electrolyte layer, and can be optionally 95% to 98%.

[0075] The weight percentage of the first adhesive in the sum of the weights of the first adhesive and the second adhesive is 15% to 100%, optionally 40% to 95%, and further optionally 50% to 75%;

[0076] The weight percentage of the second adhesive in the sum of the weights of the first adhesive and the second adhesive is 0% to 85%, optionally 5% to 60%, and further optionally 25% to 50%.

[0077] By controlling one or more of the following parameters within the aforementioned ranges: the weight percentage of the first binder in the first binder layer, the weight percentage of the second binder in the first binder layer, the weight percentage of the first binder in the first electrolyte layer, the sum of the weight percentages of the first and second binders in the first electrolyte layer, the weight percentage of the sulfide solid electrolyte in the first electrolyte layer, the percentage of the weight of the first binder in the sum of the weights of the first and second binders, and the percentage of the weight of the second binder in the sum of the weights of the first and second binders, the synergistic effect between the first and second binders can be better utilized. This is beneficial for better leveraging the low water absorption characteristic of the first binder and the dispersing and binding effects of the second binder, further improving the component dispersion uniformity and material stability of the solid electrolyte membrane, and better utilizing the role of the second binder in improving the electrochemical performance of solid-state batteries, including improving battery cycle performance. Furthermore, solid-state batteries also exhibit good ion transport performance, thus achieving good battery kinetics.

[0078] In some embodiments, the first adhesive layer comprises a cyclic olefin / chain olefin copolymer, and further comprises one or more of polyvinylidene fluoride, nitrile rubber, styrene-butadiene rubber, hydrogenated nitrile rubber, natural rubber, etherified cellulose, polymethyl methacrylate, and polyoxyethylene methyl vinyl silicone rubber.

[0079] By controlling the first layer binder to include cyclic olefin / chain olefin copolymers, the water absorption of the first electrolyte layer can be significantly reduced. By further including other types of binders mentioned above, the synergy between multiple binders can further improve the component dispersion uniformity and material stability of the solid electrolyte membrane, and better leverage the role of the second binder in improving the electrochemical performance of the solid-state battery.

[0080] In some embodiments, the sulfide solid electrolyte includes one or more of the following: LGPS type sulfide electrolyte, silver-germanium sulfide type sulfide electrolyte, lithium sulfide-phosphorus pentasulfide complex sulfide electrolyte, and thio-LISICON sulfide electrolyte.

[0081] In some embodiments, the sulfide solid electrolyte includes Li 6-x PS 5-x Cl 1+x , where 0≤x≤0.9.

[0082] When selecting the aforementioned types of sulfide solid electrolytes, the aforementioned improvement effects can be achieved.

[0083] By doping chlorine (Cl) into sulfide solid electrolytes, chlorine (Cl) can replace a portion of sulfur (S), which helps to further reduce the release of hydrogen sulfide gas from sulfide solid electrolytes in aqueous environments (such as air).

[0084] In some embodiments, the thickness of the first electrolyte layer is 15 μm to 75 μm, and can be selected as 25 μm to 50 μm.

[0085] By controlling the thickness of the first electrolyte layer within the aforementioned range, it is possible to promote the first binder to better exert the aforementioned improvement effect while also taking into account the ion transport performance between the first electrode layer and the second electrode layer.

[0086] In a second aspect of this application, an electrolyte electrode is provided, comprising an electrode body and a solid electrolyte membrane located on at least one side of the electrode body; the solid electrolyte membrane is the solid electrolyte membrane described in the first aspect of this application.

[0087] Alternatively, the electrolyte electrode may include an electrode body and a first electrolyte layer located on at least one side of the electrode body, wherein the first electrolyte layer is the first electrolyte layer defined in the first aspect of this application.

[0088] The electrolyte electrode includes an electrode body and a first electrolyte layer located on at least one side of the electrode body. As previously mentioned, the low water absorption properties of the first binder in the first electrolyte layer can reduce the amount of hydrogen sulfide released by the electrolyte electrode in a water-containing environment (such as air).

[0089] On the other hand, the aforementioned electrolyte electrode containing the first binder is beneficial to improving the stability of the material and structure, which in turn helps to maintain good ionic conductivity, and further, it is more beneficial to improve the electrochemical performance stability of solid-state batteries.

[0090] On the other hand, the improved air stability of the electrolyte electrode and the solid-state battery including the electrolyte electrode can improve the quality stability of the solid-state battery.

[0091] In some embodiments, the electrolyte electrode is a negative electrolyte electrode, and the electrode body is a negative electrode body;

[0092] Optionally, the negative electrode body includes a negative electrode current collector and a negative electrode active material layer located on at least one side of the negative electrode current collector, wherein the first electrolyte layer is located on the side of the negative electrode active material layer away from the negative electrode current collector.

[0093] The electrolyte electrode can be selected as the electrolyte negative electrode. In this case, the first electrolyte layer can be placed on the side of the negative electrode layer in the solid-state battery, which is beneficial to improve the interface stability between the negative electrode layer and the solid electrolyte layer, thereby improving the cycle performance of the solid-state battery.

[0094] In a third aspect of this application, a solid-state battery is provided, comprising at least one of a first electrolyte layer as defined in the first aspect of this application, a solid electrolyte membrane as described in the second aspect of this application, and an electrolyte electrode as described in the third aspect of this application.

[0095] In some embodiments, a solid-state battery is provided, comprising a first electrode layer, a solid electrolyte layer, and a second electrode layer stacked sequentially; wherein the solid electrolyte layer is a first electrolyte layer located on the side of the solid electrolyte layer closer to the first electrode layer.

[0096] In some embodiments, the first electrolyte layer includes a first solid electrolyte and a first binder, the first solid electrolyte including a sulfide solid electrolyte, and the first binder including a first binder; the first binder satisfies one or both of the following characteristics:

[0097] (t1) The water absorption rate of the first adhesive is less than or equal to 0.1%;

[0098] (t2) The first binder comprises a cyclic olefin / chain olefin copolymer, wherein the monomer units of the cyclic olefin / chain olefin copolymer include cyclic olefin monomer units and chain olefin monomer units, and the chain backbone of the cyclic olefin / chain olefin copolymer includes a cyclic structure provided by the cyclic olefin monomer units.

[0099] In some embodiments, the first electrolyte layer is as defined in the first aspect of this application.

[0100] The solid-state battery provided in the third aspect includes the aforementioned first electrolyte layer. In addition to the sulfide solid electrolyte, the first electrolyte layer also incorporates a first binder with low water absorption rate, which can reduce the absorption of water by the solid electrolyte layer in the solid-state battery, reduce the probability of contact reaction between the sulfide solid electrolyte and water, reduce or inhibit the decomposition of the sulfide solid electrolyte, and significantly reduce the amount of hydrogen sulfide released by the solid-state battery in a water-containing environment (such as air).

[0101] On the other hand, as the probability of contact reaction between sulfide solid electrolyte and water decreases, the material stability of sulfide solid electrolyte can be improved, which is conducive to giving full play to the fast ion conduction characteristics of sulfide solid electrolyte and keeping the solid electrolyte membrane with good ionic conductivity.

[0102] On the other hand, as the probability of contact reaction between sulfide solid electrolyte and water decreases, the stability of related materials in electrolyte electrodes and solid-state batteries, including the solid electrolyte membrane, is also improved, which can improve the electrochemical performance stability of solid-state batteries and improve battery cycle performance.

[0103] On the other hand, when using a solid electrolyte membrane to prepare a solid-state battery, it may be difficult to avoid contact with moisture in the air during operation. When using the aforementioned solid electrolyte membrane including the first electrolyte layer to prepare a solid-state battery, the probability of degradation of sulfide solid electrolyte during operation can be reduced, the air stability of the solid electrolyte membrane, electrolyte electrode and solid-state battery can be improved, and the quality stability of the solid-state battery can be improved.

[0104] The improvement described in any part of the context of this application is not intended to be limited to any theory.

[0105] In some embodiments, the solid electrolyte layer includes the first electrolyte layer and a second electrolyte layer, the second electrolyte layer being located between the second electrode layer and the first electrolyte layer;

[0106] The second electrolyte layer includes a second solid electrolyte and optionally includes a second binder.

[0107] In some embodiments, the solid-state battery satisfies one or more of the following characteristics:

[0108] The total thickness of the solid electrolyte layer is greater than or equal to 55 μm, and can be selected as 60 μm to 110 μm;

[0109] The thickness of the second electrolyte layer is greater than or equal to 30 μm, and can be selected as 35 μm to 60 μm;

[0110] The thickness of the second electrolyte layer is greater than the thickness of the first electrolyte layer;

[0111] The content of the second binder in the second electrolyte layer is lower than the content of the first binder in the first electrolyte layer, by weight percentage;

[0112] The second adhesive layer has a weight percentage of 0 wt% to 2 wt% in the second electrolyte layer;

[0113] The second solid electrolyte accounts for 98 wt% to 100 wt% of the weight of the second electrolyte layer.

[0114] By controlling the thickness of the solid electrolyte layer and / or the second electrolyte layer as described above, it is beneficial to reduce the risk of short circuits and improve the reliability of solid-state batteries.

[0115] By setting a solid electrolyte layer that includes both a first electrolyte layer and a second electrolyte layer, solid electrolyte sublayers composed of different materials can be flexibly set to achieve complementary advantages. The first electrolyte layer located between the second electrolyte layer and the first electrode layer can reduce the hydrogen sulfide release of the overall solid electrolyte layer. The presence of binder in the first electrolyte layer can also improve the adhesion strength between the first electrolyte layer and the adjacent first electrode layer, which is beneficial to improving interface stability and thus improving the electrochemical performance stability of solid-state batteries, such as improving cycle performance.

[0116] By controlling the binder content in the second electrolyte layer to be lower than that in the first electrolyte layer, the second electrolyte layer can provide higher ionic conductivity, allowing the solid electrolyte layer to both improve the adhesion strength between the first electrolyte layer and the first electrode layer and fully utilize the fast ion transport properties of the second electrolyte layer.

[0117] By controlling the thickness of the second electrolyte layer to be greater than that of the first electrolyte layer, and further controlling the second electrolyte layer to have a lower binder content, the solid electrolyte layer can simultaneously improve the adhesion strength between the first electrolyte layer and the first electrode layer and fully utilize the fast ion transport properties of the second electrolyte layer.

[0118] In some embodiments, the solid-state battery satisfies one or more of the following characteristics:

[0119] The first electrode layer is a negative electrode layer, and the second electrode layer is a positive electrode layer; optionally, the negative electrode layer includes a negative electrode current collector and a negative electrode active material layer located on at least one side of the negative electrode current collector, and the first electrolyte layer is located on the side of the negative electrode active material layer away from the negative electrode current collector;

[0120] The solid-state battery is an all-solid-state battery.

[0121] By placing the first electrolyte layer on one side of the negative electrode layer, it is beneficial to improve the adhesion and interface stability between the negative electrode layer and the solid electrolyte layer, reduce the interface impedance between the negative electrode layer and the solid electrolyte layer, and thus improve the cycle performance of the solid-state battery.

[0122] In some embodiments of the fourth aspect of this application, a method for preparing a solid electrolyte membrane is provided, comprising the following steps:

[0123] An electrolyte slurry comprising a first solid electrolyte, a first binder, and an organic solvent is prepared; wherein the first solid electrolyte comprises a sulfide solid electrolyte, and the first binder comprises a first binder;

[0124] The electrolyte slurry is coated onto a film-forming substrate and dried to form a solid electrolyte membrane on the film-forming substrate.

[0125] In some embodiments, the first adhesive satisfies one or both of the following characteristics:

[0126] (t1) The water absorption rate of the first adhesive is less than or equal to 0.1%;

[0127] (t2) The first binder comprises a cyclic olefin / chain olefin copolymer, wherein the monomer units of the cyclic olefin / chain olefin copolymer include cyclic olefin monomer units and chain olefin monomer units, and the chain backbone of the cyclic olefin / chain olefin copolymer includes a cyclic structure provided by the cyclic olefin monomer units.

[0128] In some embodiments, the solid electrolyte membrane preparation method produces the solid electrolyte membrane described in the first aspect of this application.

[0129] In some embodiments, the first electrolyte layer is as defined in the first aspect of this application.

[0130] The prepared solid electrolyte membrane has the advantages of the aforementioned solid electrolyte membrane.

[0131] In a fifth aspect of this application, a method for preparing a solid-state battery is provided, comprising the following steps:

[0132] An electrolyte electrode sheet is prepared; wherein the electrolyte electrode sheet includes a first electrode layer and a first electrolyte layer located on at least one side of the first electrode layer; wherein the first electrolyte layer includes a first solid electrolyte and a first binder layer, the first solid electrolyte including a sulfide solid electrolyte, and the first binder layer including a first binder.

[0133] A second electrode layer is formed on the side of the first electrolyte layer away from the first electrode layer.

[0134] In some embodiments, the first adhesive satisfies one or both of the following characteristics:

[0135] (t1) The water absorption rate of the first adhesive is less than or equal to 0.1%;

[0136] (t2) The first binder comprises a cyclic olefin / chain olefin copolymer, wherein the monomer units of the cyclic olefin / chain olefin copolymer include cyclic olefin monomer units and chain olefin monomer units, and the chain backbone of the cyclic olefin / chain olefin copolymer includes a cyclic structure provided by the cyclic olefin monomer units.

[0137] In some embodiments, the electrolyte electrode is as defined in the second aspect of this application, or the first electrolyte layer is as defined in the first aspect of this application.

[0138] In some embodiments, the electrolyte slurry further includes a second binder having a water absorption rate of ≥0.5%.

[0139] The solid-state battery prepared includes the advantages of the aforementioned solid-state batteries.

[0140] In some embodiments, the first electrolyte layer is formed on at least one side of the first electrode layer by coating and drying an electrolyte slurry;

[0141] The electrolyte slurry comprises the first solid electrolyte, the first layer binder, and an organic solvent.

[0142] In some embodiments, the electrolyte electrode sheet is prepared by a method comprising the following steps: coating the electrolyte slurry onto at least one surface of the first electrode sheet and drying it to obtain the electrolyte electrode sheet; wherein the first electrode sheet forms the first electrode layer and the dried electrolyte slurry forms the first electrolyte layer.

[0143] When forming the first electrolyte layer using a wet process with an electrolyte slurry, introducing a first binder with low water absorption can reduce the water absorption of the electrolyte slurry, decrease the probability of contact reaction between the sulfide solid electrolyte and water, and reduce or inhibit the decomposition of the sulfide solid electrolyte. This reduces the release of hydrogen sulfide and the stability of the sulfide solid electrolyte during the preparation of the electrolyte electrode, and also improves the material stability of the electrolyte electrode, which is beneficial to improving the quality stability of the solid-state battery obtained in further preparation. Furthermore, the release of hydrogen sulfide from the solid-state battery prepared based on this electrolyte electrode in a water-containing environment (such as air) can be correspondingly reduced.

[0144] In some embodiments, the electrolyte electrode is an electrolyte negative electrode, and the method for preparing the solid-state battery includes the following steps:

[0145] The electrolyte slurry is coated onto at least one surface of the negative electrode sheet and dried to prepare the electrolyte negative electrode sheet; wherein the negative electrode sheet forms a negative electrode layer, and the dried electrolyte slurry forms the first electrolyte layer;

[0146] A second electrolyte layer and a positive electrode layer are formed sequentially on the side of the first electrolyte layer away from the negative electrode layer.

[0147] In some embodiments, the dielectric constant ε of the organic solvent in the electrolyte slurry satisfies: ε≤6.5.

[0148] In some embodiments, the organic solvent in the electrolyte slurry satisfies one or more of the following characteristics:

[0149] The organic solvent includes one or more of low-polarity solvents and non-polar solvents; wherein, the dielectric constant ε1 of the low-polarity solvent satisfies: 2.6 < ε1 ≤ 6.5; and the dielectric constant ε2 of the non-polar solvent satisfies: ε2 ≤ 2.6.

[0150] The organic solvent includes substituted benzene, wherein the phenyl group in the substituted benzene is replaced by one or more substituents selected from the substituent group G, the substituent group G including: methyl, chlorine atom and methoxy;

[0151] The organic solvent with a dielectric constant less than or equal to 6.5 is present in a weight percentage of 50 wt% to 100 wt%, optionally 70 wt% to 100 wt%.

[0152] The organic solvent includes one or more of toluene, xylene, butyl butyrate, octyl butyrate, trimethylbenzene, toluene, chlorobenzene, dimethyl carbonate, ethyl acetate, n-hexane, anisole, dibromomethane, triethyl phosphate, isopropyl ether, and benzyl acetate; optionally, the organic solvent includes one or more of p-xylene, pseudotrimethylbenzene, toluene, butyl butyrate (butyl butyrate may include one or more of n-butyl butyrate, isobutyl isobutyrate, etc.), and octyl butyrate;

[0153] The organic solvent in the electrolyte slurry is 30 wt% to 90 wt%, and optionally 40 wt% to 70 wt%.

[0154] For electrolyte slurry systems containing the aforementioned organic solvents, selecting low-polarity or non-polar solvents can reduce side reactions with highly reactive sulfide solid electrolytes.

[0155] In some embodiments, the method for preparing the solid-state battery satisfies one or more of the following characteristics:

[0156] The electrolyte electrode sheet is the electrolyte electrode sheet described in the second aspect of this application, and the first electrode layer includes a corresponding electrode body;

[0157] The solid-state battery prepared is the solid-state battery described in the third aspect of this application.

[0158] In a sixth aspect of this application, an electrical device is provided, comprising at least one of the solid electrolyte membrane described in the first aspect of this application, the electrolyte electrode described in the second aspect of this application, the solid-state battery described in the third aspect of this application, the solid electrolyte membrane prepared by the method for preparing the solid electrolyte membrane described in the fourth aspect of this application, and the solid-state battery prepared by the method for preparing the solid-state battery described in the fifth aspect of this application.

[0159] Details of one or more embodiments or examples of this application are set forth in the following drawings and description. Other features, objects, and advantages of this application will become apparent from the specification, drawings, and claims. Attached Figure Description

[0160] To better describe and illustrate the embodiments, examples, or models provided in this application, reference may be made to one or more accompanying drawings. Additional details or examples used to describe the drawings should not be considered as limiting the scope of any of the disclosed applications, the currently described embodiments, examples, or models, or the best mode of these applications as currently understood. It should also be noted that the drawings are drawn in a simplified form and are only used to facilitate and clarify the illustration of this application. The various dimensions of each component shown in the drawings are arbitrarily shown and may be precise or not drawn to scale. For example, the dimensions of components are appropriately exaggerated in some places in the drawings to make the illustration clearer. Unless otherwise specified, the components in the drawings are not drawn to scale. The drawings of this application do not limit every dimension of every component. Furthermore, the same reference numerals are used to denote the same components throughout all the drawings. In the drawings:

[0161] Figure 1 is a schematic diagram of the structure of an electrolyte electrode sheet according to an embodiment of this application. The electrolyte electrode sheet includes an electrode body and a first electrolyte layer.

[0162] Figure 2 is a schematic diagram of the structure of an electrolyte electrode sheet according to an embodiment of the present application. The electrolyte electrode sheet includes an electrode body and a first electrolyte layer. The electrode body includes a current collector and an electrode active material layer. The electrode active material layer is located between the current collector and the first electrolyte layer. The electrolyte electrode sheet includes a current collector and an electrode active material layer and a first electrolyte layer sequentially disposed on one side of the current collector.

[0163] Figure 3 is a schematic diagram of the structure of an electrolyte negative electrode sheet according to an embodiment of the present application. The electrolyte negative electrode sheet includes a negative electrode body and a first electrolyte layer.

[0164] Figure 4 is a schematic diagram of the structure of an electrolyte negative electrode sheet according to an embodiment of this application. The electrolyte negative electrode sheet includes a negative electrode layer and a first electrolyte layer.

[0165] Figure 5 is a schematic diagram of the structure of an electrolyte negative electrode sheet according to an embodiment of the present application. The electrolyte negative electrode sheet includes a negative electrode current collector and a negative electrode active material layer and a first electrolyte layer sequentially disposed on one side of the negative electrode current collector; wherein, the negative electrode current collector and the negative electrode active material layer are contained in the negative electrode body or contained in the negative electrode layer.

[0166] Figure 6 is a schematic diagram of the structure of a solid-state battery cell according to an embodiment of this application. The solid-state battery cell includes a first electrode layer, a solid electrolyte layer and a second electrode layer stacked in sequence.

[0167] Figure 7 is a schematic diagram of the structure of a solid-state battery cell according to an embodiment of the present application. The solid-state battery cell includes a first electrode layer, a solid electrolyte layer and a second electrode layer stacked in sequence. The solid electrolyte layer includes a first electrolyte layer, which is located on the side close to the first electrode layer.

[0168] Figure 8 is a schematic diagram of the structure of a solid-state battery cell according to an embodiment of this application. The solid-state battery cell includes a first electrode layer, a first electrolyte layer, a second electrolyte layer, and a second electrode layer stacked sequentially.

[0169] Figure 9 is a schematic diagram of the structure of a solid-state battery cell according to an embodiment of this application. The solid-state battery cell includes a negative electrode layer, a solid electrolyte layer and a positive electrode layer stacked in sequence.

[0170] Figure 10 is a schematic diagram of the structure of a solid-state battery cell according to an embodiment of the present application. The solid-state battery cell includes a negative electrode layer, a first electrolyte layer, a second electrolyte layer and a positive electrode layer stacked in sequence, wherein the first electrolyte layer and the second electrolyte layer constitute a solid electrolyte layer.

[0171] Figure 11 is a schematic diagram of a solid-state battery cell according to an embodiment of this application.

[0172] Figure 12 is an exploded view of a solid-state battery cell according to an embodiment of this application, as shown in Figure 11.

[0173] Figure 13 is a schematic diagram of a battery device according to an embodiment of this application.

[0174] Figure 14 is a schematic diagram of a battery pack according to one embodiment of this application.

[0175] Figure 15 is an exploded view of a battery pack according to an embodiment of this application, as shown in Figure 14.

[0176] Figure 16 is a schematic diagram of an electrical device using a solid-state battery as a power source according to an embodiment of this application.

[0177] Explanation of reference numerals in the attached drawings: 310, first electrolyte layer; 93, electrolyte electrode sheet; 901, electrode body; 910, current collector; 920, electrode active material layer; 13, electrolyte negative electrode sheet; 101, negative electrode body; 110, negative electrode current collector; 120, negative electrode active material layer; 10, first electrode layer; 320, second electrolyte layer; 20, second electrode layer; 100, negative electrode layer; 300, solid electrolyte layer; 200, positive electrode layer; 1, battery pack; 2, upper casing; 3, lower casing; 4, battery assembly; 5, solid-state battery cell; 51, casing; 52, solid-state battery cell; 53, cover plate; 6, power-consuming device. Detailed Implementation

[0178] The following describes in detail, with appropriate reference to the accompanying drawings, some embodiments of the solid electrolyte membrane, electrolyte electrode, solid-state battery, preparation method, and electrical device provided in this application. However, some unnecessary details may be omitted. For example, detailed descriptions of well-known matters and repetitive descriptions of practically identical structures may be omitted. This is to avoid unnecessarily lengthy descriptions and to facilitate understanding by those skilled in the art. Furthermore, the accompanying drawings and the following description are provided to enable those skilled in the art to fully understand this application and are not intended to limit the subject matter of the claims.

[0179] The "range" disclosed in this application can be defined in the form of a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, which define the boundaries of a particular range. Ranges defined in this way can include or exclude endpoints. Any endpoint can be included or excluded independently and can be combined arbitrarily; that is, any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a specific parameter, it is expected that ranges of 60-110 and 80-120 are also included. Furthermore, if minimum range values ​​1 and 2 are listed, and maximum range values ​​3, 4, and 5 are also listed, then the following ranges are all expected: 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5. In this application, unless otherwise stated, the numerical range "ab" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0-5" indicates that all real numbers between "0" and "5" have been listed in this article; "0-5" is simply a shortened representation of these numerical combinations. Furthermore, when describing a parameter as an integer ≥ 2, it is equivalent to listing integers such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, and 12 for that parameter. For instance, when describing a parameter as an integer selected from "2-10", it is equivalent to listing the integers 2, 3, 4, 5, 6, 7, 8, 9, and 10.

[0180] In this application, unless otherwise specified, "about" means within a reasonable range above and below the stated number, and the range of fluctuation may vary depending on the type and value of the stated number. For example, a range of ±10%, ±5%, ±2%, ±1%, etc., may be allowed. For example, taking "about 20°C" and its approximation as ±1°C, approximate values ​​such as 19°C, 19.5°C, etc., within the approximation range indicated by "about 20°C" should also be included in the range indicated by "about 20°C".

[0181] In this application, the terms "multiple," "various," "multiple items," "several," etc., unless otherwise specified, refer to a quantity greater than or equal to 2. For example, "one or more" means one or more (greater than or equal to) two. It can be understood that when "any number of" items are involved, it refers to any suitable combination of multiple items, that is, a combination of "any number of" items in a manner that does not conflict and enables the implementation of this application.

[0182] Unless otherwise specified, all embodiments and optional embodiments of this application can be combined to form new technical solutions.

[0183] In this document, the term "embodiment" means that a particular feature, structure, or characteristic described in connection with an embodiment may be included in at least one embodiment or implementation of this application. The appearance of this phrase in various places throughout the specification does not necessarily refer to the same embodiment, nor is it a separate or alternative embodiment mutually exclusive with other embodiments. It will be explicitly and implicitly understood by those skilled in the art that the embodiments described herein can be combined with other embodiments. The term "implementation" as used herein has a similar understanding.

[0184] Those skilled in the art will understand that the order in which the steps are written in the various implementations or embodiments does not imply a strict execution order and does not constitute any limitation on the implementation process. The detailed execution order of each step should be determined by its function and possible internal logic. Unless otherwise specified, all steps in this application may be performed sequentially or randomly, but are preferably performed sequentially. For example, if method M includes steps (a) and (b), it means that method M may include steps (a) and (b) performed sequentially, or it may include steps (b) and (a) performed sequentially. As another example, method M may also include step (c), meaning that step (c) can be added to method M in any order. For example, method M may include steps (a), (b), and (c), or it may include steps (a), (c), and (b), or it may include steps (c), (a), and (b), etc.

[0185] In this application, open-ended technical features or solutions described using terms such as "containing," "including," or "comprising" do not exclude additional members beyond those listed unless otherwise specified. They can be considered as providing both closed-ended features or solutions comprised of the listed members and open-ended features or solutions that include additional members beyond the listed members. For example, if A includes a1, a2, and a3, it may also include other members or exclude additional members unless otherwise specified. This can be considered as providing both features or solutions where "A consists of a1, a2, and a3" or "A is selected from a1, a2, and a3," and features or solutions where "A includes not only a1, a2, and a3, but also other members."

[0186] In this application, unless otherwise stated, A (e.g., B) means that B is a non-limiting example of A, and it is understood that A is not limited to B.

[0187] In this application, "optionally," "optionally," and "optional" mean that something is optional, that is, it is selected from either "with" or "without." If multiple "options" appear in a technical solution, unless otherwise specified and there are no contradictions or mutual constraints, each "option" is independent. Unless otherwise specified, the descriptions such as "optionally include" and "optionally contain" in this application, taking "optionally include" as an example, mean "may include or not include."

[0188] In this application, unless otherwise specified, the features or solutions corresponding to "and / or" include any one of two or more of the related listed items, as well as any and all combinations of the related listed items. These arbitrary and all combinations include any two related listed items, any more related listed items, or a combination of all related listed items. For example, "A and / or B" represents a group consisting of A, B, and "a combination of A and B". "Containing A and / or B" can mean "containing A, containing B, and containing A and B", or "containing A, containing B, or containing A and B", and can be appropriately understood according to the context.

[0189] The terms “combinations of,” “any combination of,” and “any combination of” used in this article include all suitable combinations of any two or more of the listed items.

[0190] In this document, the term "suitable" as used in "suitable combination", "suitable method", "any suitable method", etc., refers to the technical solution that enables the implementation of this application.

[0191] In this document, terms such as "preferred," "better," "more suitable," "ideal," "good," and "superior" are merely descriptions of more effective implementation methods or embodiments, and should be understood not to limit the scope of protection of this application. If multiple "preferred" terms appear in a technical solution, unless otherwise specified and there are no contradictions or mutual constraints, each "preferred" term shall be independent.

[0192] In this application, terms such as "further," "even more," "especially," "for example," "as," "example," and "exemplary" are used for descriptive purposes to indicate differences in content, but should not be construed as limiting the scope of protection of this application.

[0193] In this application, the terms "first aspect," "second aspect," "third aspect," "fourth aspect," etc., are used for descriptive purposes only and should not be construed as indicating or implying relative importance or quantity, nor should they be construed as implicitly indicating the importance or quantity of the indicated technical features. Moreover, "first," "second," "third," "fourth," etc., serve only as a non-exhaustive enumeration and should be understood not to constitute a closed limitation on quantity.

[0194] In this application, the term "room temperature" generally refers to 4℃ to 35℃, and may refer to 20℃ ± 5℃. In some embodiments of this application, room temperature refers to 20℃ to 30℃.

[0195] In this application, if the unit for a data range is only followed by the right endpoint, it indicates that the units for the left and right endpoints are the same. For example, 3~5h or 3-5h both mean that the unit for the left endpoint "3" and the right endpoint "5" is h (hours), and both have the same meaning as 3h~5h. Furthermore, similar descriptions of other parameters such as temperature and size are interpreted in the same way.

[0196] In this application, "wt%" means weight percentage or mass percentage.

[0197] In this application, "greater than or equal to" and "≥" have the same meaning and can be used interchangeably; "less than or equal to" and "≤" have the same meaning and can be used interchangeably; "greater than" can be equivalently represented as ">", and "less than" can be equivalently represented as "<". In this application, unless otherwise specified, "greater than or equal to" and "≥" can be considered as providing two additional solutions: "greater than" and "equal to". In this application, unless otherwise specified, "less than or equal to" and "≤" can be considered as providing two additional solutions: "less than" and "equal to".

[0198] In this application, the exemplary descriptions such as "in some implementations (or embodiments)" and "in one implementation (or embodiment)" may cover, but are not limited to, the following meanings: these solutions can be combined with other solutions in a suitable manner to form new technical solutions.

[0199] Unless otherwise specified, the term "solid-state battery" in this application refers to a battery in which the electrolyte includes a solid electrolyte. Typically, a solid-state battery includes a positive electrode layer, a solid electrolyte layer, and a negative electrode layer. During charging and discharging, active ions repeatedly insert and extract between the positive and negative electrode layers. The solid electrolyte layer acts as a conductor of ions between the positive and negative electrode layers and also isolates them, preventing short circuits. Therefore, solid-state batteries do not require the separator found in traditional lithium-ion batteries. The introduction of a non-flammable solid electrolyte in solid-state batteries, replacing the organic electrolyte in traditional liquid lithium-ion batteries, significantly improves battery safety. In addition to enhanced safety, solid-state batteries are better suited for high-energy-density positive and negative electrode materials and reduce system weight, thus facilitating improvements in energy density.

[0200] In this application, unless otherwise specified, "solid electrolyte" refers to an electrolyte material or substance that exists in solid form during the storage and fabrication of solid-state batteries and their components, as well as during the operation of solid-state batteries. This includes, but is not limited to, solid electrolytes existing in solid form at room temperature.

[0201] In this application, unless otherwise specified, the electrode layer can be a positive electrode layer or a negative electrode layer, and the electrode layer includes electrode active materials. The electrode active materials can be positive electrode active materials or negative electrode active materials. The electrode active materials can be particulate matter themselves or contained within electrode active particles. The electrode active particles can be positive electrode active particles or negative electrode active particles. "Electrode active material" in the electrode layer refers to a material capable of reversibly inserting and extracting active ions. Unless otherwise specified, "negative electrode active material" refers to a material used in the negative electrode layer capable of reversibly inserting and extracting active ions; "positive electrode active material" refers to a material used in the positive electrode layer capable of reversibly extracting and inserting active ions. When the solid-state battery is charged, active ions are extracted from the positive electrode, pass through the solid electrolyte layer, and insert into the negative electrode; while when the solid-state battery is discharged, active ions are extracted from the negative electrode and insert into the positive electrode. The active ions are not particularly limited or restrictive; they can be lithium ions, corresponding to a lithium-ion solid-state battery.

[0202] In this application, "electrode active particles" refers to particles containing electrode active substances.

[0203] In this application, unless otherwise specified, "electrode active material layer" includes at least one of the positive electrode active material layer in the positive electrode layer and the negative electrode active material layer in the negative electrode layer. Depending on the specific circumstances, the electrode active material layer may refer to either the positive electrode active material layer or the negative electrode active material layer. It is understood that the positive electrode active material layer contains a positive electrode active substance, and the negative electrode active material layer contains a negative electrode active substance. In this application, "electrode active material layer" may also be abbreviated as "active material layer".

[0204] In this application, the terms "first," "second," "first adhesive," "second adhesive," "first solid electrolyte," and "second solid electrolyte," etc., are used for descriptive purposes only and should not be construed as indicating or implying relative importance or quantity, nor should they be construed as implicitly indicating the importance or quantity of the indicated technical features. Moreover, "first," "second," etc., serve only as a non-exhaustive enumeration and should be understood not to constitute a closed limitation on quantity.

[0205] Among numerous solid electrolyte materials, sulfide solid electrolytes stand out due to their extremely high ionic conductivity (e.g., up to approximately 10). -3 ~10 - 2 Sulfide solid electrolytes possess excellent mechanical properties, such as good flexibility, which gives them superior ion conduction and deformation capabilities, making them one of the most promising solid electrolyte materials for practical application and industrialization. However, the chemical stability in aqueous atmospheres is one of the most serious problems facing sulfide solid electrolytes. Water in the air reacts with sulfides to produce highly toxic and harmful hydrogen sulfide gas, further accelerating the degradation of sulfides and severely restricting the practical application of sulfide solid electrolytes.

[0206] Based on this, according to various embodiments and examples of this application, this application provides a solid electrolyte membrane, an electrolyte electrode, a solid-state battery, a preparation method, and an electrical device, and further provides a solid electrolyte membrane and its preparation method, an electrolyte electrode, a solid-state battery and its preparation method, and an electrical device. The hydrogen sulfide release from this solid electrolyte membrane, electrolyte electrode, and solid-state battery in an aqueous environment is significantly reduced.

[0207] In some embodiments, the solid electrolyte membrane includes a first electrolyte layer comprising a sulfide solid electrolyte and a binder, the binder comprising a first binder with low water absorption (e.g., water absorption ≤ 0.1%). The electrolyte electrode comprises an electrode body and a solid electrolyte membrane located on at least one side of the electrode body, or comprises an electrode body and a first electrolyte layer located on at least one side of the electrode body. The solid-state battery comprises at least one of a first electrolyte layer, a solid electrolyte membrane, and an electrolyte electrode. The solid electrolyte membrane, electrolyte electrode, and solid-state battery exhibit significantly reduced hydrogen sulfide release in aqueous environments.

[0208] In some embodiments of the first aspect of this application, a solid electrolyte membrane is provided, which includes a first electrolyte layer, the first electrolyte layer including a sulfide solid electrolyte and a binder (which may be referred to as a first layer binder), the binder (i.e. the first layer binder) including a first binder;

[0209] Furthermore, the first adhesive may satisfy one or more of the following characteristics:

[0210] (t1) The water absorption rate of the first adhesive is ≤0.1%;

[0211] (t2) The first binder includes a cyclic olefin / chain olefin copolymer, wherein the monomer units of the cyclic olefin / chain olefin copolymer include cyclic olefin monomer units and chain olefin monomer units, and the chain backbone of the cyclic olefin / chain olefin copolymer includes a cyclic structure provided by the cyclic olefin monomer units.

[0212] In this application, unless otherwise specified, the binder included in the first electrolyte layer may be referred to as "first layer binder".

[0213] In some embodiments, a solid electrolyte membrane is provided, comprising a first electrolyte layer, the first electrolyte layer comprising a first solid electrolyte and a first binder layer; wherein the first solid electrolyte comprises a sulfide solid electrolyte; the first binder layer comprises a first binder, optionally having a water absorption rate of less than or equal to 0.1%.

[0214] In some embodiments, the first binder comprises a cyclic olefin / chain olefin copolymer, wherein the monomer units of the cyclic olefin / chain olefin copolymer include cyclic olefin monomer units and chain olefin monomer units, and the chain backbone of the cyclic olefin / chain olefin copolymer includes a cyclic structure provided by the cyclic olefin monomer units.

[0215] In some embodiments, a solid electrolyte membrane is provided, comprising a first electrolyte layer, the first electrolyte layer comprising a sulfide solid electrolyte and a first binder layer, the first binder layer comprising a first adhesive.

[0216] The first binder includes a cyclic olefin / chain olefin copolymer, wherein the monomer units of the cyclic olefin / chain olefin copolymer include cyclic olefin monomer units and chain olefin monomer units, and the chain backbone of the cyclic olefin / chain olefin copolymer includes a cyclic structure provided by the cyclic olefin monomer units.

[0217] In this application, the "first adhesive" is an adhesive with low water absorption, which may have a water absorption rate of ≤0.1%. The first adhesive may include cyclic olefin / chain olefin copolymers with low water absorption, for example, cyclic olefin / chain olefin copolymers with a water absorption rate of ≤0.1%.

[0218] Unless otherwise specified in this application, the water absorption rate of the adhesive can be tested using the following method: Water absorption rate of adhesive materials is tested using the specific gravity method according to national standard GB / T 1037. More specifically, the following method can be used for testing:

[0219] (1) Weigh and record the actual mass M1 of the absorbent paper, and then put it into the drying room; after standing for a period of time (e.g., more than or equal to 2 hours), weigh the mass of the adhesive material and record it as M2;

[0220] (2) Centrifuge for 5 minutes to remove surface moisture from the material. The rotation speed is greater than or equal to 1000 rpm, for example, 1000 rpm to 1500 rpm.

[0221] (3) Take out the absorbent paper and record its actual mass, weigh it together with the adhesive and record the mass M3;

[0222] (4) Calculate the water absorption rate (ω) according to the following formula: ω=(M1+M3-M2) / M2.

[0223] In this application, the test of the water absorption rate of the adhesive is conducted at a temperature in the range of 20°C to 30°C, for example, 23±2°C, unless otherwise specified.

[0224] In this application, the test temperature for the water absorption rate of the adhesive is described as "the water absorption rate of the first adhesive is ≤0.1% at 23±2℃". As long as a temperature exists within the range of 23±2℃, it is acceptable to measure the water absorption rate of the first adhesive as ≤0.1%. "23±2℃" means that the temperature can be controlled at any temperature between 21℃ and 25℃.

[0225] Those skilled in the art can identify the types and structures of components in solid-state batteries using one or more of the following detection methods, including but not limited to: Fourier transform infrared (FT-IR) spectroscopy, ultraviolet spectroscopy, and proton nuclear magnetic resonance (NMR) spectroscopy. 1 H NMR (1H NMR) method, carbon nuclear magnetic resonance (NMR) spectroscopy 13Methods include C10 NMR, X-ray diffraction (XRD), gel permeation chromatography (GPC), high-performance liquid chromatography (HPLC), mass spectrometry, inductively coupled plasma atomic emission spectrometry (ICP), and energy dispersive spectroscopy (EDS). Non-limitingly, one or more of the following methods can be used to analyze the type, structure, and molecular weight of the binder components in solid-state batteries: Fourier transform infrared (FT-IR) spectroscopy, proton nuclear magnetic resonance (NMR) spectroscopy, and so on. 1 H NMR (1H NMR) method, carbon nuclear magnetic resonance (NMR) spectroscopy 13 Methods include C NMR, gel permeation chromatography (GPC), ultraviolet-visible spectroscopy (UV-vis), thermogravimetric analysis (TGA) or micro-quotient thermogravimetric analysis (DTG), differential scanning calorimetry (DSC), dynamic thermomechanical analysis (DMA), and viscosity testing. The sample preparation and testing methods for these methods are known to those skilled in the art, and the test parameters can be appropriately adjusted according to the sample characteristics.

[0226] In this application, unless otherwise specified, "cyclic olefin / chain olefin copolymer" refers to a copolymer comprising at least two monomer units, including both cyclic olefin monomer units and chain olefin monomer units, wherein the chain backbone of the cyclic olefin / chain olefin copolymer includes a cyclic structure provided by the cyclic olefin monomer units. This copolymer can be an addition copolymer of the corresponding cyclic olefin monomer and a monomer containing an α-olefin group, and can be prepared through an addition copolymerization reaction of the corresponding monomers. In the addition copolymer composed of cyclic olefin monomer units and chain olefin monomer units, the cyclic structure of the cyclic olefin monomer is retained in the main chain of the copolymer, resulting in the chain backbone of the cyclic olefin / chain olefin copolymer including a cyclic structure provided by the cyclic olefin monomer units. In the solid state, the chain backbone of the cyclic olefin / chain olefin copolymer facilitates the formation of an ordered and closely packed structure, which helps reduce the voids where water molecules can enter, making it difficult for water molecules to penetrate, thereby giving the cyclic olefin / chain olefin copolymer a low water absorption rate. Furthermore, for addition copolymers, the chain skeleton of cyclic olefin / chain olefin copolymers can be a carbon skeleton, that is, it can be composed of carbon atoms. Therefore, the carbon skeleton may not contain functional groups that have strong interactions with water, which is also beneficial to reducing the water absorption rate of olefin / chain olefin copolymers.

[0227] In this application, unless otherwise specified, the “chain skeleton” of a cyclic olefin / chain olefin copolymer refers to the chain structure formed by the copolymerization reaction of reactive carbon-carbon double bonds in each monomer, which connects the monomers through carbon atoms at the reaction sites.

[0228] In this application, unless otherwise specified, "cyclic olefin monomer unit" refers to the divalent group formed after the cyclic olefin monomer participates in copolymerization. "Cyclic olefin monomer" refers to a cyclic monomer that includes a cyclic structure, wherein at least one cyclic structure contains a reactive carbon-carbon double bond, and the cyclic structure containing the reactive carbon-carbon double bond participates in constituting the chain backbone of the cyclic olefin / chain olefin copolymer. Non-limiting examples of cyclic olefin monomers include norbornene, cyclopentene, cyclohexene, cycloheptene, etc.

[0229] In this application, unless otherwise specified, "chain olefin monomer unit" refers to the divalent group formed after the chain olefin monomer participates in copolymerization. Unless otherwise specified, "chain olefin monomer" refers to a monomer containing an α-alkenyl group, whose residues, after copolymerization, provide the linear carbon chain portion in the copolymer. The chain olefin monomer can be an aliphatic monomer. Non-limiting examples of monomers containing an α-alkenyl group include α-olefins. Non-limiting examples of chain olefin monomers include ethylene, propylene, etc.

[0230] In this application, unless otherwise specified, "divalent group" refers to a group having two covalent linkage sites.

[0231] By introducing a first binder with low water absorption rate into the solid electrolyte membrane containing a sulfide solid electrolyte, the absorption of water by the solid electrolyte membrane can be reduced, the probability of contact reaction between the sulfide solid electrolyte and water can be decreased, and the decomposition of the sulfide solid electrolyte can be reduced or inhibited, thus significantly reducing the amount of hydrogen sulfide released by the solid electrolyte membrane in an aqueous environment (such as air). Furthermore, the amount of hydrogen sulfide released by the electrolyte electrode and solid-state battery prepared based on this solid electrolyte membrane in an aqueous environment (such as air) can be correspondingly reduced.

[0232] On the other hand, as the probability of contact reaction between sulfide solid electrolyte and water decreases, the material stability of sulfide solid electrolyte can be improved, which is conducive to giving full play to the fast ion conduction characteristics of sulfide solid electrolyte and maintaining good ionic conductivity of solid electrolyte membrane.

[0233] On the other hand, as the probability of contact reaction between sulfide solid electrolyte and water decreases, the stability of related materials in electrolyte electrodes and solid-state batteries, including the solid electrolyte membrane, is also improved, which can improve the electrochemical performance stability of solid-state batteries.

[0234] On the other hand, when using a solid electrolyte membrane to prepare a solid-state battery, it may be difficult to avoid contact with moisture in the air during operation. When using the aforementioned solid electrolyte membrane, which includes a first electrolyte layer, to prepare a solid-state battery, the probability of degradation of sulfide solid electrolyte during operation can be reduced, the air stability of the solid electrolyte membrane, electrolyte electrode and solid-state battery can be improved, and the quality stability of the solid-state battery can be improved.

[0235] The improvement described in any part of the context of this application is not intended to be limited to any theory.

[0236] The cyclic olefin / chain olefin copolymers involved in this application can be obtained commercially or prepared by free radical copolymerization between cyclic olefin monomers and chain olefin monomers.

[0237] In some implementations, the first adhesive satisfies one or more of the following characteristics (any numerical parameter of the following characteristics may also be selected from any suitable value or range in the context):

[0238] The chain backbone of cyclic olefin / chain olefin copolymers is a carbon backbone;

[0239] Cyclic olefin / chain olefin copolymers are aliphatic polymers;

[0240] Cyclic structures in cyclic olefin monomer units include one or more of monocyclic and polycyclic structures;

[0241] The number of ring atoms in the cyclic olefin monomer unit is 3 to 30, and can be selected as 5 to 20;

[0242] Alkene monomer units include those corresponding to C 2～6 The structural unit of olefins;

[0243] The side groups of cyclic olefin / chain olefin copolymers include C 1～10 Aliphatic chains and fluorinated C 1～10 One or more of the aliphatic chains;

[0244] In the cyclic olefin / chain olefin copolymer, the molar fraction of cyclic olefin monomer units is 10% to 85%, optionally 30% to 85%, and further optionally 50% to 85%;

[0245] In the cyclic olefin / chain olefin copolymer, the molar fraction of chain olefin monomer units is 15% to 90%, optionally 15% to 70%, and further optionally 15% to 50%;

[0246] The weight-average molecular weight of the cyclic olefin / chain olefin copolymer is 30kDa to 100kDa, and can be selected as 30kDa to 50kDa.

[0247] In some embodiments, the first adhesive satisfies one or more of the following characteristics:

[0248] The number of ring atoms in the cyclic structure of cyclic olefin monomers ranges from 5 to 20.

[0249] Cycloolefin monomer units include structural units corresponding to one or more monomers such as norbornene, cyclopentene, cyclohexene, and cycloheptene;

[0250] The olefin monomer unit includes structural units corresponding to one or more monomers of ethylene and propylene; optionally, the olefin monomer unit includes structural units corresponding to ethylene.

[0251] The side groups of cyclic olefin / chain olefin copolymers include C 1～10 Alkyl chains and fluorinated C 1～10 One or more of the alkyl chain;

[0252] In cyclic olefin / chain olefin copolymers, the molar fraction of cyclic olefin monomer units is 50% to 85%;

[0253] In cyclic olefin / chain olefin copolymers, the molar fraction of chain olefin monomer units is 15% to 50%;

[0254] The weight-average molecular weight of cyclic olefin / chain olefin copolymers is 30 kDa to 50 kDa.

[0255] In some embodiments, the chain backbone of the cyclic olefin / chain olefin copolymer is a carbon backbone. In this case, the chain backbone of the cyclic olefin / chain olefin copolymer can be composed of carbon atoms, without functional groups that form strong interactions with water, which is beneficial for reducing the water absorption rate of the cyclic olefin / chain olefin copolymer.

[0256] In some embodiments, the cyclic olefin / chain olefin copolymer is an aliphatic polymer.

[0257] In this application, unless otherwise stated, "aliphatic polymer" refers to a polymer that does not contain an aromatic structure and does not contain an aromatic ring.

[0258] When the cyclic olefin / chain olefin copolymer is an aliphatic polymer, the molecule does not contain aromatic rings, which is beneficial for the cyclic olefin / chain olefin copolymer to have a more suitable dielectric constant. When preparing slurries containing non-polar or low-polar solvents, it is beneficial for improving the dispersion uniformity of the slurry system.

[0259] In some embodiments, the cyclic structure in the cyclic olefin monomer unit includes one or more of monocyclic and polycyclic structures.

[0260] In this application, unless otherwise specified, "monocyclic" refers to a closed ring formed by the sequential connection of ring-forming atoms, without any adjacent rings sharing a ring-forming atom; "polycyclic structure" refers to a structure comprising multiple rings, including adjacent rings sharing at least one ring-forming atom. A non-limiting example of a polycyclic structure is a bridged ring. A "bridged ring" refers to a ring-containing structure in which at least one group of adjacent rings shares two or more ring-forming atoms. A non-limiting example of a bridged ring is a cyclic structure in norbornene or its residues.

[0261] In this application, the term "ring-forming atom" refers to the atom that constitutes the ring framework. It is understood that the ring-forming atom is not a hydrogen atom.

[0262] In some embodiments, the number of ring atoms in the cyclic structure of the cyclic olefin monomer unit is 3 to 30, optionally 5 to 20, and may also be any of the following values ​​or a range selected from any two of the following values: 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 24, 25, 26, 28, 30, etc.

[0263] In some embodiments, the cyclic olefin monomer unit may include structural units corresponding to one or more monomers such as norbornene, cyclopentene, cyclohexene, and cycloheptene. In some embodiments, the cyclic olefin monomer unit may include structural units corresponding to norbornene.

[0264] In some embodiments, the olefinic monomer unit includes a component corresponding to C 2～6 The structural unit of an olefin chain. C 2～6 Non-limiting examples of olefins include ethylene, propylene, butene, pentene, and hexene. In some embodiments, the olefin monomer unit may include a structural unit corresponding to one or more monomers such as ethylene and propylene. Further, the olefin monomer unit may include a structural unit corresponding to ethylene.

[0265] In some embodiments, the side groups of the cyclic olefin / chain olefin copolymer may include C 1～10 Aliphatic chains and fluorinated C 1～10 One or more aliphatic chains.

[0266] In some embodiments, the side groups of the cyclic olefin / chain olefin copolymer may include one or more aliphatic chains and fluorinated aliphatic chains. In some embodiments, the side groups of the cyclic olefin / chain olefin copolymer may be selected from C 1～10 Aliphatic chains and fluorinated C 1～10 One or more aliphatic chains.

[0267] In this application, "aliphatic chain" refers to a chain that does not contain an aromatic ring, "C 1～10 "Aliphatic chain" refers to an aliphatic chain with 1 to 10 carbon atoms. 1～10 The number of carbon atoms in an aliphatic chain can be 1 to 10, or any of the following values ​​or a range selected from any two of the following values: 1, 23, 4, 5, 6, 7, 8, 9, or 10. C 1～10 Aliphatic chains can be C 1～8 Aliphatic chains, further optionally C 1～6 Aliphatic chains, and even more specifically C1～3 Aliphatic chains.

[0268] In this application, "fluorinated aliphatic chain" refers to an aliphatic chain in which at least one hydrogen atom is replaced by a fluorine atom, and the number of fluorine atoms can be one or more; "fluorinated C 1～10 An aliphatic chain is an aliphatic chain having 1 to 10 carbon atoms and at least one hydrogen atom replaced by a fluorine atom. The number of fluorine atoms can be one or more.

[0269] In some embodiments, the aliphatic chain is an alkyl chain.

[0270] In some embodiments, the fluorinated aliphatic chain is a fluorinated alkyl chain.

[0271] In some embodiments, the side groups of the cyclic olefin / chain olefin copolymer may include one or more of alkyl chains and fluoroalkyl chains.

[0272] In some implementations, C 1～10 Aliphatic chains can be C 1～10 A hydrocarbon chain, meaning it contains only carbon and hydrogen atoms; furthermore, C 1～10 Aliphatic chains can be C 1～10 Alkyl chain.

[0273] In some implementations, C 1～10 Aliphatic chains can be fluorinated C 1～10 A hydrocarbon chain, that is, containing only carbon atoms, fluorine atoms, and optional hydrogen atoms, where the hydrogen atoms may be partially or completely replaced by fluorine atoms; furthermore, C 1～10 Aliphatic chains can be fluorinated C 1～10 Alkyl chain.

[0274] In some embodiments, the side groups of the cyclic olefin / chain olefin copolymer may include C 1～10 Alkyl chains and fluorinated C 1～10 One or more alkyl chains. In some embodiments, the side groups of the cyclic olefin / chain olefin copolymer may be selected from C. 1～10 Alkyl chains and fluorinated C 1～10 One or more of the alkyl chain.

[0275] In this application, "C" 1～10 "Alkyl chain" refers to an alkyl chain having 1 to 10 carbon atoms. This can be understood as C... 1～10 The alkyl chain does not contain unsaturated bonds.

[0276] In this application, "fluorinated C" 1～10 "Alkyl chain" refers to an alkyl chain having 1 to 10 carbon atoms and fluorine atoms. The number of fluorine atoms can be one or more, and hydrogen atoms can be partially or completely replaced by fluorine atoms.

[0277] In this application, unless otherwise specified, "alkyl" means a monovalent residue formed by the loss of a hydrogen atom from a saturated hydrocarbon containing a primary (normal) carbon atom, or a secondary carbon atom, or a tertiary carbon atom, or a quaternary carbon atom, or a combination thereof. Phrases containing this term, such as "C1-8 alkyl," refer to alkyl groups containing 1 to 8 carbon atoms, and each occurrence may independently be C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, or C8 alkyl. Suitable examples include, but are not limited to: methyl (Me, -CH3), ethyl (Et, -CH2CH3), 1-propyl (n-Pr, n-propyl, -CH2CH2CH3), 2-propyl (i-Pr, i-propyl, -CH(CH3)2), 1-butyl (n-Bu, n-butyl, -CH2CH2CH2CH3), 2-methyl-1-propyl (i-Bu, i-butyl, -CH2CH(CH3)2), 2-butyl (s-Bu, s-butyl, -CH(CH3)2) )CH2CH3), 2-methyl-2-propyl (t-Bu, t-butyl, -C(CH3)3), 1-pentyl (n-pentyl, -CH2CH2CH2CH2CH3), 2-pentyl (-CH(CH3)CH2CH2CH3), 3-pentyl (-CH(CH2CH3)2), 2-methyl-2-butyl (-C(CH3)2CH2CH3), 3-methyl-2-butyl (-CH(CH3)CH(CH3)2), 3-methyl-1-butyl (-CH2C) H2CH(CH3)2), 2-methyl-1-butyl(-CH2CH(CH3)CH2CH3), 1-hexyl(-CH2CH2CH2CH2CH2CH3), 2-hexyl(-CH(CH3)CH2CH2CH2CH3), 3-hexyl(-CH(CH2CH3)(CH2CH2CH3)), 2-methyl-2-pentyl(-C(CH3)2CH2CH2CH3), 3-methyl-2-pentyl(-CH(CH3)CH(CH3)CH 2CH3), 4-methyl-2-pentyl (-CH(CH3)CH2CH(CH3)2), 3-methyl-3-pentyl (-C(CH3)(CH2CH3)2), 2-methyl-3-pentyl (-CH(CH2CH3)CH(CH3)2), 2,3-dimethyl-2-butyl (-C(CH3)2CH(CH3)2), 3,3-dimethyl-2-butyl (-CH(CH3)C(CH3)3), octyl (-(CH2)7CH3), 2-ethyl-hexyl, etc.

[0278] In a non-limiting manner, the molar fraction of cyclic olefin monomer units in the cyclic olefin / chain olefin copolymer can be 10% to 85%, optionally 30% to 85%, further optionally 50% to 85%, and can also be any of the following percentages or a range selected from any two of the following percentages: 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, etc.

[0279] Non-limitingly, in the cyclic olefin / chain olefin copolymer, the molar fraction of the chain olefin monomer unit is 15% to 90%, optionally 15% to 70%, further optionally 15% to 50%, and may also be any of the following percentages or a range selected from any two of the following percentages: 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, etc.

[0280] Non-limitingly, the weight-average molecular weight of the cyclic olefin / chain olefin copolymer can be 30kDa to 100kDa, optionally 30kDa to 50kDa, further optionally 35kDa to 40kDa, and can also be any of the following molecular weights or a range selected from any two of the following molecular weights: 30kDa, 35kDa, 40kDa, 45kDa, 50kDa, 60kDa, 70kDa, 80kDa, 90kDa, 100kDa, etc.

[0281] In this application, the terms "molecular weight," "average molecular weight," "weight-average molecular weight," "relative atomic mass," or "relative molecular mass" used to refer to adhesives or polymers, unless otherwise specified, refer to molecular mass measured in Daltons (Da), where 1 Dalton equals... 12 One-twelfth the mass of a carbon atom. 1 kDa = 1000 Da.

[0282] In this application, "weight-average molecular weight" has a well-known meaning in the polymer field, which is the sum of the weight fraction of molecules of different molecular weights multiplied by their corresponding molecular weights.

[0283] The molecular weight of polymers (such as adhesives) can be obtained using conventional methods in the polymer field, such as gel permeation chromatography (GPC), high performance liquid chromatography (HPLC), and mass spectrometry.

[0284] By adjusting one or more parameters, such as the type and size of the rings in the cyclic olefin monomer unit, the number of carbon atoms in the chain olefin monomer unit, the mole fraction of the cyclic olefin monomer unit, the mass fraction of the cyclic olefin monomer unit, the mole fraction of the chain olefin monomer unit, the mass fraction of the chain olefin monomer unit, and the weight-average molecular weight of the cyclic olefin / chain olefin copolymer, one or more of the following can be adjusted: the flexibility or rigidity of the cyclic olefin / chain olefin copolymer, the viscosity of the electrolyte slurry, and the dispersing effect on sulfide solid electrolytes. As a non-limiting example, increasing the content of cyclic olefin monomer units can increase molecular rigidity, increasing the content of chain olefin monomer units can increase molecular flexibility, increasing the weight-average molecular weight can increase the viscosity of the electrolyte slurry, and adjusting the adhesion and dielectric constant can regulate the dispersing effect on sulfide solid electrolytes.

[0285] On the other hand, the water absorption characteristics of cyclic olefin / chain olefin copolymers can be adjusted by regulating the ratio between cyclic olefin monomer units and chain olefin monomer units. The higher the proportion of cyclic olefin monomer units, the more beneficial it is to reduce the water absorption rate.

[0286] When the side groups of the cyclic olefin / chain olefin copolymer include fluorinated groups (such as fluorinated aliphatic chains, or even fluorinated alkyl chains), it is beneficial to improve the fluidity of the slurry and further improve the dispersion uniformity of the slurry.

[0287] By adjusting one or more of the aforementioned parameters within the aforementioned range, it is more beneficial to improve at least one of the following items: low water absorption of cyclic olefin / chain olefin copolymers, material stability of sulfide solid electrolytes, dispersion stability of electrolyte slurry, coating uniformity of electrolyte slurry, and dispersion uniformity of electrolyte slurry.

[0288] In some embodiments, the cyclic olefin / chain olefin copolymer includes one or more of (ethylene-cyclopentene) copolymers, (ethylene-norbornene) random copolymers, and (ethylene-norbornene) alternating copolymers.

[0289] The water absorption rate of (ethylene-cyclopentene) copolymer, (ethylene-norbornene) random copolymer and (ethylene-norbornene) alternating copolymer can be controlled within the range of 0.01% to 0.1%.

[0290] The aforementioned types of cyclic olefin / chain olefin copolymers can better control at least one of the following: the low water absorption characteristics of cyclic olefin / chain olefin copolymers, the material stability of sulfide solid electrolytes, the dispersion stability of electrolyte slurries, the coating uniformity of electrolyte slurries, and the dispersion uniformity of electrolyte slurries.

[0291] In some embodiments, the water absorption rate of the first adhesive is less than or equal to 0.1%, optionally less than or equal to 0.05%; further optionally, the water absorption rate of the first adhesive is less than or equal to 0.02%; and even more optionally, the water absorption rate of the first adhesive is less than or equal to 0.01%.

[0292] Non-limitingly, the water absorption rate of the first adhesive may also be any of the following percentages, or less than or equal to any of the following percentages, or selected from a range consisting of any two of the following percentages: 0.1%, 0.09%, 0.08%, 0.07%, 0.06%, 0.05%, 0.04%, 0.03%, 0.02%, 0.01%, 0.006%, 0.005%, 0.004%, 0.002%, 0.001%, 0.0005%, 0.0001%, etc.

[0293] By controlling the water absorption rate of the first binder within the aforementioned range, the water absorption of the solid electrolyte membrane can be further reduced, which is more conducive to reducing or inhibiting the decomposition of sulfide solid electrolytes and can better reduce the release of hydrogen sulfide from solid electrolyte membranes, electrolyte electrodes and solid batteries in water-containing environments (such as air).

[0294] On the other hand, by controlling the water absorption rate of the first binder within the aforementioned range, it is more conducive to suppressing the decomposition of sulfides, more conducive to improving the material stability of sulfide solid electrolytes, and more conducive to maintaining good ionic conductivity of the solid electrolyte membrane; furthermore, it is more conducive to improving the electrochemical performance stability of solid-state batteries.

[0295] On the other hand, by controlling the water absorption rate of the first binder within the aforementioned range, it is more beneficial to reduce the degradation probability of the sulfide solid electrolyte during the preparation of solid-state batteries using a solid electrolyte membrane including the first electrolyte layer. This is beneficial to further improve the air stability of the solid electrolyte membrane, electrolyte electrode and solid-state battery, and can improve the quality stability of solid-state batteries.

[0296] Non-limitingly, in the first electrolyte layer, the weight percentage of the first binder in the first layer binder can be 15% to 100%, optionally 40% to 95%, further optionally 40% to 90%, even more preferably 50% to 75%, and can also be any of the following percentages or a range selected from any two of the following percentages: 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 100%, etc. Non-limitingly, the weight percentage of the first binder in the first layer binder can also be selected from any suitable range of the following: 15% to 95%, 15% to 90%, 30% to 95%, 30% to 90%, 40% to 90%, 40% to 75%, etc.

[0297] Non-limitingly, in the first electrolyte layer, the weight percentage of the first binder in the first electrolyte layer can be 0.3% to 6%, optionally 0.3% to 4%, more preferably 0.5% to 2%, and can also be any of the following percentages or a range selected from any two of the following percentages: 0.3%, 0.4%, 0.5%, 0.6%, 0.8%, 1%, 1.2%, 1.5%, 1.6%, 1.8%, 2%, 2.2%, 2.4%, 2.5%, 2.6%, 2.8%, 3%, 3.2%, 3.5%, 3.6%, 3.8%, 4%, 4.5%, 5%, 5.5%, 6%, etc. Non-limitingly, the weight percentage of the first binder in the first electrolyte layer can also be selected from any suitable range: 0.3% to 1.8%, etc.

[0298] Non-limitingly, the weight percentage of the sulfide solid electrolyte in the first electrolyte layer may be 94% to 99.5%, optionally 95% to 98%, or any of the following percentages or a range selected from any two of the following percentages: 94%, 94.5%, 95%, 95.5%, 96%, 96.5%, 97%, 97.5%, 98%, 98.5%, 99%, 99.5%, etc.

[0299] In some embodiments, the first electrolyte layer satisfies one or more of the following characteristics (any numerical parameter of the following characteristics may also be selected from any suitable value or range in the context):

[0300] The first adhesive has a weight percentage of 15% to 100% in the first layer of adhesive, optionally 40% to 95%, further optionally 40% to 90%, and even more preferably 50% to 75%;

[0301] The first binder comprises 0.3% to 6% by weight in the first electrolyte layer, optionally 0.3% to 4%, and further optionally 0.5% to 2%.

[0302] The sulfide solid electrolyte has a weight percentage of 94% to 99.5% in the first electrolyte layer, and can be optionally 95% to 98%.

[0303] In some embodiments, the first electrolyte layer satisfies one or more of the following characteristics (any numerical parameter of the following characteristics may also be selected from any suitable value or range in the context):

[0304] The weight percentage of the first adhesive in the first layer of adhesive is 25% to 75%;

[0305] The weight percentage of the first binder in the first electrolyte layer is 0.5% to 2%;

[0306] The sulfide solid electrolyte accounts for 95% to 98% by weight in the first electrolyte layer.

[0307] By controlling one or more parameters among the following within the aforementioned ranges—the weight percentage of the first binder in the first layer of binder, the weight percentage of the first binder in the first electrolyte layer, and the weight percentage of the sulfide solid electrolyte in the first electrolyte layer—it is advantageous to reduce hydrogen sulfide release, improve the material stability of the sulfide solid electrolyte, and also enable the solid electrolyte membrane to have higher ionic conductivity.

[0308] In some embodiments, the first electrolyte layer further includes a second binder having a water absorption rate greater than or equal to 0.5%, optionally greater than or equal to 1%, further optionally greater than or equal to 2%, and further optionally greater than or equal to 5%.

[0309] Non-limitingly, the water absorption rate of the second adhesive may also be any of the following percentages, or greater than or equal to any of the following percentages, or greater than or equal to any of the following percentages and less than or equal to 10%, or selected from the range of any two of the following percentages: 0.5%, 0.6%, 0.8%, 1%, 1.2%, 1.5%, 1.6%, 1.8%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 6%, 7%, 8%, etc.

[0310] In some embodiments, the first electrolyte layer includes a first adhesive and a second adhesive. Non-limitingly, the second adhesive may include one or more of nitrile rubber, styrene-butadiene rubber, hydrogenated nitrile rubber, natural rubber, etherified cellulose, polymethyl methacrylate, polyethylene oxide methyl vinyl silicone rubber, and derivatives of any of the foregoing. It is understood that derivatives of any of the foregoing still fall within the scope of the second adhesive. For example, the water absorption rate of the derivative may be ≥0.5%, optionally greater than or equal to 1%, further optionally greater than or equal to 2%, and may also be any of the following percentages, or greater than or equal to any of the following percentages, or selected from any two of the following percentages: 0.5%, 0.6%, 0.8%, 1%, 1.2%, 1.5%, 1.6%, 1.8%, 2%, etc.

[0311] In this application, the "second adhesive" is an adhesive with a higher water absorption rate than the first adhesive. For example, the water absorption rate of the second adhesive may be ≥0.5%, optionally greater than or equal to 1%, further optionally greater than or equal to 2%, and may also be any of the following percentages, or greater than or equal to any of the following percentages, or selected from any two of the following percentages: 0.5%, 0.6%, 0.8%, 1%, 1.2%, 1.5%, 1.6%, 1.8%, 2%, etc.

[0312] In some embodiments, the second adhesive may include at least one selected from nitrile rubber and nitrile rubber derivatives, wherein the nitrile rubber derivative may include hydrogenated nitrile rubber. In some embodiments, the second adhesive may be selected from at least one selected from nitrile rubber and nitrile rubber derivatives, wherein the nitrile rubber derivative may be hydrogenated nitrile rubber.

[0313] Typically, the water absorption rate of nitrile rubber, styrene-butadiene rubber, hydrogenated nitrile rubber, natural rubber, etherified cellulose, polymethyl methacrylate, and polyethylene oxide methyl vinyl silicone rubber can be 0.5% to 10%.

[0314] By incorporating the aforementioned type of second binder into the first electrolyte layer, it is beneficial to reduce hydrogen sulfide release and improve the material stability of the sulfide solid electrolyte. Simultaneously, it allows for better control of the dispersion uniformity, dispersion stability, and coating uniformity of the slurry system in the first electrolyte layer. This, in turn, improves the component distribution uniformity of the first electrolyte layer and the uniformity and stability of the electrical contact network. From this perspective, it is beneficial to improve the electrochemical performance of solid-state batteries, such as, but not limited to, improving their cycle performance. Furthermore, utilizing the excellent low water absorption characteristics provided by the first binder can significantly reduce the water absorption problems that are easily caused by introducing the second binder, greatly suppressing the battery performance degradation that may result from water absorption by the first binder. The synergistic effect between the first and second binders can further improve the component dispersion uniformity and material stability of the solid electrolyte membrane, allowing the second binder to better enhance the electrochemical performance of the solid-state battery.

[0315] Taking nitrile rubber (NBR) as an example, NBR has good film-forming properties as a binder material; however, it has a relatively high water absorption rate (e.g., about 0.5%). When solid electrolyte membranes containing NBR and sulfide solid electrolytes are exposed to air, a large amount of toxic hydrogen sulfide gas is released, further accelerating the degradation of sulfides and reducing the ionic conductivity of the sulfide solid electrolyte, affecting the electrochemical performance of the subsequently fabricated solid-state battery. This results in high manufacturing costs due to the need to control the moisture content in the air. By introducing a first binder with low water absorption, the release of hydrogen sulfide can be effectively reduced, improving the air stability of the sulfide solid electrolyte, the solid electrolyte membrane containing the sulfide solid electrolyte, the electrolyte electrode, and the solid-state battery.

[0316] Non-limitingly, in the first electrolyte layer, the weight percentage of the second binder in the first binder layer can be 0% to 85%, optionally 5% to 60%, further optionally 10% to 60%, and even more preferably 25% to 50%, and can also be any of the following percentages or a range selected from any two of the following percentages: 0%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, etc. Non-limitingly, the weight percentage of the second binder in the first binder layer can also be selected from any suitable range of the following: 5% to 85%, 10% to 85%, 5% to 70%, 10% to 70%, 10% to 60%, 25% to 60%, etc.

[0317] Non-limitingly, the sum of the weight percentages of the first adhesive and the second adhesive in the first electrolyte layer can be 0.5% to 6%, optionally 2% to 5%, or any of the following percentages or a range selected from any two of the following percentages: 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, etc. Non-limitingly, the sum of the weight percentages of the first adhesive and the second adhesive in the first electrolyte layer can also be selected from any suitable range: 0.5% to 5%, 1% to 3%, etc.

[0318] Non-limitingly, in the first electrolyte layer, the percentage of the weight of the first binder in the sum of the weights of the first binder and the second binder can be 15% to 100%, optionally 40% to 95%, further optionally 40% to 90%, even more preferably 50% to 75%, and can also be any of the following percentages or a range selected from any two of the following percentages: 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 100%, etc. Non-limitingly, the percentage of the weight of the first binder in the sum of the weights of the first binder and the second binder can also be selected from any suitable range of the following: 15% to 95%, 15% to 90%, 30% to 95%, 30% to 90%, 40% to 90%, 40% to 75%, etc.

[0319] Non-limitingly, in the first electrolyte layer, the percentage of the weight of the second binder in the sum of the weights of the first binder and the second binder can be 0% to 85%, optionally 5% to 60%, further optionally 10% to 60%, and even more preferably 25% to 50%, or any of the following percentages or a range selected from any two of the following percentages: 0%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, etc. Non-limitingly, the percentage of the weight of the second binder in the sum of the weights of the first binder and the second binder can also be selected from any suitable range of the following: 5% to 85%, 10% to 85%, 5% to 70%, 10% to 70%, 10% to 60%, 25% to 60%, etc.

[0320] In some embodiments, the first electrolyte layer satisfies one or more of the following characteristics (any numerical parameter of the following characteristics may also be selected from any suitable value or range in the context):

[0321] The second adhesive comprises 0% to 85% by weight of the first adhesive layer, optionally 5% to 60%, and further optionally 25% to 50%.

[0322] The sum of the weight percentages of the first binder and the second binder in the first electrolyte layer is 0.5% to 6%, and more preferably 2% to 5%;

[0323] The weight percentage of the first adhesive in the sum of the weights of the first adhesive and the second adhesive is 15% to 100%, optionally 40% to 95%, further optionally 40% to 90%, and even more preferably 50% to 75%.

[0324] The weight percentage of the second adhesive in the sum of the weights of the first adhesive and the second adhesive is 0% to 85%, optionally 5% to 60%, further optionally 10% to 60%, and even more preferably 25% to 50%.

[0325] In some embodiments, the first electrolyte layer satisfies one or more of the following characteristics (any numerical parameter of the following characteristics may also be selected from any suitable value or range in the context):

[0326] The first adhesive comprises 15% to 100% by weight in the first layer of adhesive, optionally 40% to 95%, and further optionally 50% to 75%.

[0327] The second adhesive comprises 0% to 85% by weight of the first adhesive layer, optionally 5% to 60%, and further optionally 25% to 50%.

[0328] The first binder comprises 0.3% to 6% by weight in the first electrolyte layer, optionally 0.3% to 4%, and further optionally 0.5% to 2%.

[0329] The sum of the weight percentages of the first binder and the second binder in the first electrolyte layer is 0.5% to 6%, and optionally 2% to 5%.

[0330] The sulfide solid electrolyte in the first electrolyte layer has a weight percentage of 94% to 99.5%, and can be optionally 95% to 98%;

[0331] The weight percentage of the first adhesive in the sum of the weights of the first adhesive and the second adhesive is 15% to 100%, optionally 40% to 95%, and further optionally 50% to 75%.

[0332] The weight percentage of the second adhesive in the sum of the weights of the first adhesive and the second adhesive is 0% to 85%, optionally 5% to 60%, and further optionally 25% to 50%.

[0333] By controlling one or more of the following parameters within the aforementioned ranges: the weight percentage of the first binder in the first binder layer, the weight percentage of the second binder in the first binder layer, the weight percentage of the first binder in the first electrolyte layer, the sum of the weight percentages of the first and second binders in the first electrolyte layer, the weight percentage of the sulfide solid electrolyte in the first electrolyte layer, the percentage of the weight of the first binder in the sum of the weights of the first and second binders, and the percentage of the weight of the second binder in the sum of the weights of the first and second binders, the synergistic effect between the first and second binders can be better utilized. This is beneficial for better leveraging the low water absorption characteristic of the first binder and the dispersing and binding effects of the second binder, further improving the component dispersion uniformity and material stability of the solid electrolyte membrane, and better utilizing the role of the second binder in improving the electrochemical performance of solid-state batteries, including improving battery cycle performance. Furthermore, solid-state batteries also exhibit good ion transport performance, thus achieving good battery kinetics.

[0334] In some embodiments, the first adhesive layer comprises a cyclic olefin / chain olefin copolymer, and also includes one or more of polyvinylidene fluoride, nitrile rubber, styrene-butadiene rubber, hydrogenated nitrile rubber, natural rubber, etherified cellulose, polymethyl methacrylate, and polyoxyethylene methyl vinyl silicone rubber.

[0335] By controlling the first layer binder to include cyclic olefin / chain olefin copolymers, the water absorption of the first electrolyte layer can be significantly reduced. By further including other types of binders mentioned above, the synergy between multiple binders can further improve the component dispersion uniformity and material stability of the solid electrolyte membrane, and better leverage the role of the second binder in improving the electrochemical performance of the solid-state battery.

[0336] In some embodiments, in solid-state batteries, solid electrolyte membranes, or electrolyte electrodes, including but not limited to, in solid electrolyte layers, including but not limited to, in a first electrolyte layer, the sulfide solid electrolyte may include at least one of binary sulfide solid systems and ternary sulfide solid systems. Non-limitingly, the binary sulfide solid system may include one or more of Li₂S-P₂S₅, Li₂S-SiS₂, Li₂S-GeS₂, and Li₂S-B₂S₃. Non-limitingly, the ternary sulfide solid system may include one or more of the following: silver sulfide-germanium sulfide electrolyte, Li2S-MeS2-P2S5 ternary sulfide electrolyte, lithium germanium phosphorus sulfide electrolyte, Li2S-P2S5-MS ternary sulfide electrolyte, Li2S-P2S5-MCl ternary sulfide electrolyte, and thio-LISICON type sulfide electrolyte; wherein, Me may include one or more elements selected from silicon (Si), germanium (Ge), tin (Sn), and aluminum (Al), and may further be selected from one or more elements selected from Si, Ge, Sn, and Al; M may include one or more elements selected from Ge, Al, Sn, lead (Pb), antimony (Sb), Si, and arsenic (As), and may further be selected from one or more elements selected from Ge, Al, Sn, Pb, Sb, Si, and As.

[0337] In some embodiments, the sulfide solid electrolyte includes one or more of the following: LGPS type sulfide electrolyte, silver-germanium sulfide type sulfide electrolyte, lithium sulfide-phosphorus pentasulfide complex sulfide electrolyte, and thio-LISICON sulfide electrolyte.

[0338] Unless otherwise specified, the sulfide electrolytes of the sulfide type have a sulfide-germanium type crystal phase structure. Without limitation, the sulfide electrolyte may include electrolytes with the chemical formula Li 6±s P 1-j A j S 5±s-t B t X 1±s The electrolyte is a sulfide electrolyte, wherein 0 ≤ j < 1, 0 ≤ t < 1, 0 ≤ s < 1, A can be selected from, but is not limited to, one or more elements selected from Ge, Si, Sn, and Sb, B can be one or more elements selected from O, Se, and Te, and X can be selected from one or more elements selected from Cl, Br, I, and F. In some embodiments, X is a halogen, and further, X can be selected from one or more elements selected from Cl, Br, I, and F.

[0339] In some embodiments, the sulfide solid electrolyte in the first electrolyte layer includes Li6PS5X, where X is a halogen, and further, X may be selected from one or more elements selected from Cl, Br and I.

[0340] Unless otherwise specified, the sulfide electrolyte of the LGPS type has a LGPS-type crystal phase structure. Without limitation, the sulfide electrolyte of the LGPS type may include a sulfide electrolyte having the chemical formula Li 10±δ5 Ge 1-g G g P 2-q Q q S 12-w W w , where 0 ≤ δ5 < 1, 0 ≤ g ≤ 1, 0 ≤ q ≤ 2, 0 ≤ w < 1, G is selected from one or both elements of Si and Sn, Q is Sb, and W is selected from one or more elements of O, Se, Te, Cl, Br, I, and F.

[0341] Without limitation, the sulfide electrolyte of the lithium sulfide-phosphorus pentasulfide complex type may include a sulfide electrolyte having the chemical formula (100 - u - v)Li2S·uP2S5·vM m N n , where 0 < u < 100, 0 ≤ v < 100, 0 ≤ u + v < 100, 0 ≤ m < 4, 0 ≤ n < 6, M may be selected from one or more elements of Li, B, Ge, Si, Sn, and Sb, and N may be selected from one or more elements of S, Se, Te, O, Cl, Br, I, and F.

[0342] In some embodiments, the sulfide solid electrolyte includes Li 6-x PS 5-x Cl 1+x , where 0 ≤ x ≤ 0.9. Non-limiting examples of x are 0, 0.05, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, and may also be selected from the ranges formed by any two of the foregoing numerical values, and may also be greater than 0 and less than or equal to any one of the foregoing non-zero numerical values.

[0343] When selecting the foregoing types of sulfide solid electrolytes, the foregoing improvement effects can be achieved.

[0344] By doping chlorine (Cl) element in the sulfide solid electrolyte, the (Cl) element can replace a part of the sulfur (S) element, which is beneficial to further reducing the hydrogen sulfide gas release amount of the sulfide solid electrolyte in a water-containing environment (such as air).

[0345] In some embodiments, the thickness of the first electrolyte layer is 15 μm to 75 μm, optionally 25 μm to 50 μm, and may also be any one of the following thicknesses or selected from the ranges formed by any two of the following thicknesses: 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, etc.

[0346] By controlling the thickness of the first electrolyte layer within the aforementioned range, it is possible to promote the first binder to better exert the aforementioned improvement effect while also taking into account the ion transport performance between the first electrode layer and the second electrode layer.

[0347] In some embodiments of the second aspect of this application, an electrolyte electrode is provided, comprising an electrode body and a solid electrolyte membrane located on at least one side of the electrode body; the solid electrolyte membrane includes a first electrolyte layer. The solid electrolyte membrane may be the solid electrolyte membrane described in the first aspect of this application.

[0348] In some implementations, the first electrolytic layer is as defined in the first aspect of this application.

[0349] In some embodiments of the second aspect of this application, an electrolyte electrode is provided, which includes an electrode body and a first electrolyte layer located on at least one side of the electrode body. The first electrolyte layer may be the first electrolyte layer defined in the first aspect of this application.

[0350] The electrolyte electrode includes an electrode body and a first electrolyte layer located on at least one side of the electrode body. As previously mentioned, the low water absorption properties of the first binder in the first electrolyte layer can reduce the amount of hydrogen sulfide released by the electrolyte electrode in a water-containing environment (such as air).

[0351] On the other hand, the aforementioned electrolyte electrode containing the first binder is beneficial to improving the stability of the material and structure, which in turn helps to maintain good ionic conductivity, and further, it is more beneficial to improve the electrochemical performance stability of solid-state batteries.

[0352] On the other hand, the improved air stability of the electrolyte electrode and the solid-state battery including the electrolyte electrode can improve the quality stability of the solid-state battery.

[0353] In some embodiments, an electrolyte electrode 93 is provided, which includes an electrode body 901 and a first electrolyte layer 310 located on at least one side of the electrode body, one example of which can be seen in FIG1.

[0354] The electrode body 901 includes at least an electrode active material layer 920.

[0355] In some embodiments, the electrode body 901 includes a current collector 910 and an electrode active material layer 920 located on at least one side of the current collector. In some embodiments, in the electrolyte electrode 93, the electrode active material layer 920 is located between the current collector 910 and the first electrolyte layer 310.

[0356] In some embodiments, the electrolyte electrode 93 includes a current collector 910 and an electrode active material layer 920 and a first electrolyte layer 310 sequentially disposed on at least one side of the current collector 910, one example of which can be seen in FIG2.

[0357] In some embodiments, an electrolyte electrode is provided, comprising an electrode body and a solid electrolyte membrane located on at least one side of the electrode body; the solid electrolyte membrane includes a first electrolyte layer. The first electrolyte layer may be as defined in the first aspect of this application.

[0358] In some embodiments, the electrode body includes a current collector and an electrode active material layer located on at least one side of the current collector, with a solid electrolyte membrane or a first electrolyte layer located on the side of the electrode active material layer away from the current collector. In this case, the electrode active material layer is located between the current collector and the solid electrolyte membrane, or the electrode active material layer is located between the current collector and the first electrolyte layer.

[0359] In some embodiments, the solid electrolyte membrane is located on the surface of the electrode active material layer away from the current collector.

[0360] In some embodiments, the electrode body includes a current collector and an electrode active material layer located on at least one side of the current collector, with the electrode active material layer disposed between the solid electrolyte membrane and the current collector.

[0361] In some embodiments, the electrode body includes a current collector and an electrode active material layer located on at least one side of the current collector, with the electrode active material layer disposed between the first electrolyte layer and the current collector.

[0362] In some embodiments, the electrolyte electrode sheet is an electrolyte negative electrode sheet, and the electrode body is a negative electrode body. Accordingly, the current collector is a negative electrode current collector, and the electrode active material layer is a negative electrode active material layer.

[0363] In some embodiments, the electrolyte electrode sheet is an electrolyte negative electrode sheet, and the electrode body is a negative electrode body; in some embodiments, the negative electrode body includes a negative electrode current collector and a negative electrode active material layer located on at least one side of the negative electrode current collector, and a first electrolyte layer is located on the side of the negative electrode active material layer away from the negative electrode current collector.

[0364] The electrolyte electrode can be selected as the electrolyte negative electrode. In this case, the first electrolyte layer can be placed on the side of the negative electrode layer in the solid-state battery, which is beneficial to improve the interface stability between the negative electrode layer and the solid electrolyte layer, thereby improving the cycle performance of the solid-state battery.

[0365] In some embodiments, an electrolyte negative electrode 13 is provided, which includes a negative electrode body 101 and a first electrolyte layer 310 located on at least one side of the negative electrode body 101. The definition of the first electrolyte layer can be found in the first aspect of this application. An example of the electrolyte negative electrode 13 can be found in FIG3.

[0366] In some embodiments, an electrolyte negative electrode sheet is provided, comprising a negative electrode body and a solid electrolyte membrane located on at least one side of the negative electrode body; the solid electrolyte membrane includes a first electrolyte layer. Further, the first electrolyte layer is located on the side of the solid electrolyte membrane closer to the negative electrode body.

[0367] In some embodiments, the negative electrode body 101 includes a negative electrode current collector 110 and a negative electrode active material layer 120 located on at least one side of the negative electrode current collector 110. Further, in the electrolyte negative electrode sheet 13, a first electrolyte layer 310 is located on the side of the negative electrode active material layer 120 away from the negative electrode current collector 110. Further, the first electrolyte layer 310 is located on the surface of the negative electrode active material layer 120 on the side away from the negative electrode current collector 110.

[0368] In some embodiments, an electrolyte negative electrode 13 is provided, which includes a negative electrode layer 100 and a first electrolyte layer 310 located on at least one side of the negative electrode layer 100, one example of which can be seen in FIG4.

[0369] In some embodiments, the negative electrode layer 100 includes a negative electrode current collector 110 and a negative electrode active material layer 120 located on at least one side of the negative electrode current collector 110. Further, the negative electrode active material layer 120 is located between the negative electrode current collector 110 and the first electrolyte layer 310.

[0370] The electrolyte electrode can be selected as the electrolyte negative electrode. In this case, the first electrolyte layer can be placed on the side of the negative electrode layer in the solid-state battery. This is beneficial to improve the adhesion between the negative electrode layer and the solid electrolyte layer, reduce the interfacial impedance between the negative electrode layer and the solid electrolyte layer, and thus improve the cycle performance of the solid-state battery.

[0371] The negative electrode layer 100 includes at least a negative electrode active material layer 120.

[0372] In some embodiments, the electrolyte negative electrode sheet 13 includes a negative electrode current collector 110 and a negative electrode active material layer 120 and a first electrolyte layer 310 sequentially disposed on at least one side of the negative electrode current collector 110, one example of which can be seen in FIG5.

[0373] In some embodiments, the first electrolyte layer or solid electrolyte membrane is located on the surface of the negative electrode active material layer away from the negative electrode current collector.

[0374] In some embodiments, an electrolyte negative electrode sheet is provided, which includes a negative electrode body and a solid electrolyte membrane located on at least one side of the negative electrode body; the solid electrolyte membrane includes a first electrolyte layer.

[0375] In some embodiments, the negative electrode body includes a negative electrode current collector and a negative electrode active material layer located on at least one side of the negative electrode current collector, and a solid electrolyte membrane is located on the surface of the negative electrode active material layer away from the negative electrode current collector. Further, the solid electrolyte membrane may be located on the surface of the negative electrode active material layer away from the negative electrode current collector.

[0376] In some embodiments of the third aspect of this application, a solid-state battery is provided, comprising at least one of a first electrolyte layer as defined in the first aspect of this application, a solid electrolyte membrane as described in the second aspect of this application, and an electrolyte electrode as described in the third aspect of this application.

[0377] In some embodiments, a solid-state battery is provided, which includes a first electrode layer, a solid electrolyte layer and a second electrode layer stacked sequentially; wherein the solid electrolyte layer includes a first electrolyte layer, and the first electrolyte layer is located on the side of the solid electrolyte layer close to the first electrode layer;

[0378] The first electrolyte layer is as defined in the first aspect of this application.

[0379] In some embodiments, the first electrolyte layer includes a first solid electrolyte and a first binder, the first solid electrolyte including a sulfide solid electrolyte, and the first binder including a first binder; the first binder satisfies one or both of the following characteristics:

[0380] (t1) The water absorption rate of the first adhesive is less than or equal to 0.1%;

[0381] (t2) The first binder includes a cyclic olefin / chain olefin copolymer, wherein the monomer units of the cyclic olefin / chain olefin copolymer include cyclic olefin monomer units and chain olefin monomer units, and the chain backbone of the cyclic olefin / chain olefin copolymer includes a cyclic structure provided by the cyclic olefin monomer units.

[0382] The solid-state battery provided in the third aspect includes the aforementioned first electrolyte layer. In addition to the sulfide solid electrolyte, the first electrolyte layer also incorporates a first binder with low water absorption rate, which can reduce the absorption of water by the solid electrolyte layer in the solid-state battery, reduce the probability of contact reaction between the sulfide solid electrolyte and water, reduce or inhibit the decomposition of the sulfide solid electrolyte, and significantly reduce the amount of hydrogen sulfide released by the solid-state battery in a water-containing environment (such as air).

[0383] On the other hand, as the probability of contact reaction between sulfide solid electrolyte and water decreases, the material stability of sulfide solid electrolyte can be improved, which is conducive to giving full play to the fast ion conduction characteristics of sulfide solid electrolyte and keeping the solid electrolyte membrane with good ionic conductivity.

[0384] On the other hand, as the probability of contact reaction between sulfide solid electrolyte and water decreases, the stability of related materials in electrolyte electrodes and solid-state batteries, including the solid electrolyte membrane, is also improved, which can improve the electrochemical performance stability of solid-state batteries and improve battery cycle performance.

[0385] On the other hand, when using a solid electrolyte membrane to prepare a solid-state battery, it may be difficult to avoid contact with moisture in the air during operation. When using the aforementioned solid electrolyte membrane including the first electrolyte layer to prepare a solid-state battery, the probability of degradation of sulfide solid electrolyte during operation can be reduced, the air stability of the solid electrolyte membrane, electrolyte electrode and solid-state battery can be improved, and the quality stability of the solid-state battery can be improved.

[0386] The improvement described in any part of the context of this application is not intended to be limited to any theory.

[0387] In some embodiments, the solid electrolyte layer includes a first electrolyte layer and a second electrolyte layer, the second electrolyte layer being located between the second electrode layer and the first electrolyte layer;

[0388] The second electrolyte layer includes a solid electrolyte (which may be referred to as the second solid electrolyte) and optionally includes a binder (which may be referred to as the second binder).

[0389] In this application, unless otherwise specified, the binder included in the second electrolyte layer may be referred to as "second layer binder".

[0390] In some embodiments, a solid-state battery is provided, comprising a first electrode layer, a solid electrolyte layer, and a second electrode layer stacked sequentially; wherein the solid electrolyte layer includes a first electrolyte layer and a second electrolyte layer, and the first electrolyte layer is located between the second electrolyte layer and the first electrode layer.

[0391] In some embodiments, a solid-state battery is provided, comprising a first electrode layer, a solid electrolyte layer, and a second electrode layer stacked sequentially; wherein the solid electrolyte layer includes a first electrolyte layer and a second electrolyte layer, and the first electrolyte layer is located between the second electrolyte layer and the first electrode layer.

[0392] In some implementations, solid-state batteries satisfy one or more of the following characteristics (any numerical parameter of the following characteristics may also be selected from any suitable value or range in the context):

[0393] The total thickness of the solid electrolyte layer is greater than or equal to 55 μm, and can be selected from 60 μm to 110 μm;

[0394] The thickness of the second electrolyte layer is greater than or equal to 30 μm, and can be selected from 35 μm to 60 μm;

[0395] The thickness of the second electrolyte layer is greater than the thickness of the first electrolyte layer;

[0396] The content of the second binder in the second electrolyte layer is lower than the content of the first binder in the first electrolyte layer, by weight percentage;

[0397] The second binder has a weight percentage of 0 wt% to 2 wt% in the second electrolyte layer;

[0398] The second solid electrolyte in the second electrolyte layer is 98 wt% to 100 wt% by weight;

[0399] The first electrolyte layer is the first electrolyte layer as defined in the first aspect of this application.

[0400] Non-limitingly, the total thickness of the solid electrolyte layer can be greater than 55 μm, and can be selected from 60 μm to 110 μm, or can be any of the following thicknesses or a range selected from any two of the following thicknesses: 55 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, etc.

[0401] Non-limiting, the thickness of the second electrolyte layer may be greater than or equal to 30 μm, and may be selected from 35 μm to 60 μm, or may be any of the following thicknesses or a range selected from any two of the following thicknesses: 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, etc.

[0402] By controlling the thickness of the solid electrolyte layer and / or the second electrolyte layer as described above, it is beneficial to reduce the risk of short circuits and improve the reliability of solid-state batteries.

[0403] In some embodiments, the thickness of the second electrolyte layer is greater than the thickness of the first electrolyte layer.

[0404] By controlling the thickness of the second electrolyte layer to be greater than that of the first electrolyte layer, and further controlling the second electrolyte layer to have a lower binder content, the solid electrolyte layer can simultaneously improve the adhesion strength between the first electrolyte layer and the first electrode layer and fully utilize the fast ion transport properties of the second electrolyte layer.

[0405] In some embodiments, the binder content in the second electrolyte layer is lower than that in the first electrolyte layer, by weight percentage.

[0406] By controlling the binder content in the second electrolyte layer to be lower than that in the first electrolyte layer, the second electrolyte layer can provide higher ionic conductivity, allowing the solid electrolyte layer to both improve the adhesion strength between the first electrolyte layer and the first electrode layer and fully utilize the fast ion transport properties of the second electrolyte layer.

[0407] Non-limitingly, the weight percentage of the second binder in the second electrolyte layer can be 0 wt% to 2 wt%, optionally 0 wt% to 1.5 wt%, further optionally 0 wt% to 1 wt%, or any of the following percentages or a range selected from any two of the following percentages: 0 wt%, 0.1 wt%, 0.2 wt%, 0.4 wt%, 0.5 wt%, 1 wt%, 1.5 wt%, 2 wt%, etc. That is, the second electrolyte layer may include a binder with a weight percentage of 0 wt% to 2 wt%, and may also select any of the aforementioned weight percentages or ranges.

[0408] In some embodiments, the weight percentage of the second solid electrolyte in the second electrolyte layer can be 98 wt% to 100 wt%, or it can be any of the following percentages or a range selected from any two of the following percentages: 98 wt%, 98.5 wt%, 99 wt%, 99.5 wt%, 100 wt%, etc.

[0409] By setting a solid electrolyte layer that includes both a first electrolyte layer and a second electrolyte layer, solid electrolyte sublayers composed of different materials can be flexibly set to achieve complementary advantages. The first electrolyte layer located between the second electrolyte layer and the first electrode layer can reduce the hydrogen sulfide release of the overall solid electrolyte layer. The presence of binder in the first electrolyte layer can also improve the adhesion strength between the first electrolyte layer and the adjacent first electrode layer, which is beneficial to improving interface stability and thus improving the electrochemical performance stability of solid-state batteries, such as improving cycle performance.

[0410] In some embodiments, the second electrolyte layer does not include the first binder.

[0411] In some implementations, the second electrolyte layer does not include an adhesive.

[0412] In some embodiments, the second electrolyte layer is composed of a solid electrolyte.

[0413] In some embodiments, the second electrolyte layer consists of a solid electrolyte and a binder (i.e., a second binder).

[0414] In some implementations...

[0415] The first electrode layer is a negative electrode layer, and the second electrode layer is a positive electrode layer; optionally, the negative electrode layer includes a negative electrode current collector and a negative electrode active material layer located on at least one side of the negative electrode current collector, and the first electrolyte layer is located on the side of the negative electrode active material layer away from the negative electrode current collector.

[0416] By placing the first electrolyte layer on one side of the negative electrode layer, it is beneficial to improve the adhesion and interface stability between the negative electrode layer and the solid electrolyte layer, reduce the interface impedance between the negative electrode layer and the solid electrolyte layer, and thus improve the cycle performance of the solid-state battery.

[0417] In some embodiments, the first electrolyte layer and the negative electrode active material layer are in contact.

[0418] In some embodiments, a solid-state battery is provided, which includes a negative electrode layer, a solid electrolyte layer and a positive electrode layer stacked sequentially; wherein the solid electrolyte layer includes a first electrolyte layer located on the side of the solid electrolyte layer closer to the negative electrode layer;

[0419] The first electrolyte layer is as defined in the first aspect of this application.

[0420] In some embodiments, the negative electrode layer includes a negative electrode current collector and a negative electrode active material layer located on at least one side of the negative electrode current collector, with the negative electrode active material layer disposed between the first electrolyte layer and the negative electrode current collector.

[0421] In some embodiments, a solid-state battery is provided, comprising a negative electrode layer, a solid electrolyte layer, and a positive electrode layer stacked sequentially; wherein the solid electrolyte layer includes a first electrolyte layer and a second electrolyte layer, the first electrolyte layer being located between the second electrolyte layer and the negative electrode layer.

[0422] In some embodiments, the first electrolyte layer includes a first solid electrolyte and a first binder, wherein the first solid electrolyte includes a sulfide solid electrolyte and the first binder includes a first binder.

[0423] In some embodiments, the first electrolyte layer includes a first solid electrolyte and a first binder, the first solid electrolyte including a sulfide solid electrolyte, and the first binder including a first binder and a second binder.

[0424] In some embodiments, the first electrolyte layer includes a sulfide solid electrolyte, a first binder, and a second binder.

[0425] In some implementations, the solid-state battery is an all-solid-state battery.

[0426] In this application, unless otherwise specified, "all-solid-state battery" refers to a solid-state battery in which all electrolytes are solid electrolytes. In this case, the positive electrode layer, negative electrode layer and electrolyte part are all made of solid materials, and no liquid electrolyte is provided in the battery, so it can be called "all-solid-state battery".

[0427] A solid-state battery includes at least one solid-state battery cell. A solid-state battery may include one or more solid-state battery cells.

[0428] In this application, unless otherwise specified, "solid-state battery cell" refers to a basic unit capable of converting chemical energy into electrical energy, and all its components are solid-state. In some embodiments, a solid-state battery cell may be an all-solid-state battery cell.

[0429] In this application, unless otherwise specified, "all-solid-state battery cell" refers to a solid-state battery cell in which all electrolytes are solid electrolytes. In this case, the positive electrode layer, negative electrode layer and electrolyte part are all made of solid materials, and no liquid electrolyte is provided in the battery cell, so it can be called "all-solid-state battery cell".

[0430] Non-limitingly, a solid-state battery cell (which can be an all-solid-state battery cell) may include a positive electrode layer, a solid electrolyte layer, and a negative electrode layer, with the solid electrolyte layer located between the positive and negative electrode layers. During battery charging and discharging, active ions shuttle between the positive and negative electrode layers, inserting and extracting. The solid electrolyte layer serves to conduct ions between the positive and negative electrode layers and also isolates them, thus preventing short circuits between the positive and negative electrodes.

[0431] In some embodiments, the solid-state battery cell 5 includes a solid-state cell 52.

[0432] In some implementations, the solid-state cell is an all-solid-state cell.

[0433] In some embodiments, the solid-state cell 52 (which may be an all-solid-state cell) includes a first electrode layer 10, a solid electrolyte layer 300, and a second electrode layer 20 stacked sequentially, one example of which is shown in FIG. 6. In some embodiments, the solid electrolyte layer 300 includes a first electrolyte layer 310 located on the side close to the first electrode layer 10, one example of which is shown in FIG. 7.

[0434] In some embodiments, the solid-state cell 52 (which may be an all-solid-state cell) includes a first electrode layer 10, a first electrolyte layer 310, and a second electrode layer 2, which are stacked sequentially.

[0435] In some embodiments, the solid-state cell 52 (which may be an all-solid-state cell) includes a first electrode layer 10, a first electrolyte layer 310, a second electrolyte layer 320 and a second electrode layer 20 stacked sequentially, one example of which can be found in FIG8.

[0436] In some embodiments, the solid-state cell 52 (which may be an all-solid-state cell) includes a negative electrode layer 100, a solid electrolyte layer 300 and a positive electrode layer 200 stacked sequentially, one example of which can be found in FIG9.

[0437] In some embodiments, the solid-state cell 52 (which may be an all-solid-state cell) includes a negative electrode layer 100, a first electrolyte layer 310, a second electrolyte layer 320 and a positive electrode layer 200 stacked sequentially, one example of which can be found in FIG10.

[0438] In some embodiments, the solid-state battery may include an outer packaging. This outer packaging can be used to encapsulate the aforementioned solid-state battery cell.

[0439] In some embodiments, the outer packaging of a solid-state battery can be a rigid shell, such as a hard plastic shell, an aluminum shell, or a steel shell. The outer packaging of a solid-state battery can also be a soft pack, such as a pouch-type soft pack. The material of the soft pack can be plastic; further, non-limiting examples of plastics may include one or more of polypropylene, polybutylene terephthalate, and polybutylene succinate.

[0440] This application does not impose any particular limitation on the shape of the solid-state battery cell; it can be cylindrical, square, or any other arbitrary shape. For example, Figure 11 shows a square solid-state battery cell 5 as an example.

[0441] In some embodiments, referring to FIG12, the outer packaging may include a housing 51 and a cover plate 53. The housing 51 may include a base plate and side plates connected to the base plate, the base plate and side plates forming a receiving cavity. The housing 51 has an opening communicating with the receiving cavity, and the cover plate 53 can be placed over the opening to close the receiving cavity. A solid-state battery cell 52 is encapsulated within the receiving cavity. The number of solid-state battery cells 52 contained in the solid-state battery cell 5 may be one or more, which can be selected by those skilled in the art according to actual needs.

[0442] Solid-state batteries can be battery device 4 or battery pack 1.

[0443] The battery device includes at least one solid-state battery cell. The number of solid-state battery cells in the battery device can be one or more, and those skilled in the art can select an appropriate number according to the application and capacity of the battery device.

[0444] Figure 13 shows a battery device 4 as an example. Referring to Figure 13, in the battery device 4, multiple solid-state battery cells 5 can be arranged sequentially along the length of the battery device 4. Of course, they can also be arranged in any other arbitrary manner. Furthermore, the multiple solid-state battery cells 5 can be fixed in place by fasteners.

[0445] Optionally, the battery device 4 may also include a housing with a receiving space in which a plurality of solid-state battery cells 5 are housed.

[0446] In some embodiments, the battery devices described above can also be assembled into a battery pack, and the number of battery devices contained in the battery pack can be one or more. Those skilled in the art can select an appropriate number according to the application and capacity of the battery pack.

[0447] Figures 14 and 15 show a battery pack 1 as an example. Referring to Figures 14 and 15, the battery pack 1 may include a battery box and a plurality of battery devices 4 disposed within the battery box. The battery box includes an upper box 2 and a lower box 3, the upper box 2 covering the lower box 3 to form a closed space for accommodating the battery devices 4. The plurality of battery devices 4 may be arranged in any manner within the battery box.

[0448] The following are some additional descriptions of the solid electrolyte layer.

[0449] The formation of the solid electrolyte layer can be found in the fourth aspect of this application, but is not limited thereto.

[0450] The solid electrolyte layer acts as a conductor of ions between the positive and negative electrode layers, and can also isolate the positive and negative electrode layers to prevent short circuits between them.

[0451] It is understood that the solid electrolyte layer includes solid electrolytes. The types of solid electrolytes in the solid electrolyte layer can be found in the context of this application.

[0452] The types of solid electrolytes present in different film layers of a solid-state battery can be the same or different. For example, the types of solid electrolytes in the positive electrode layer and the solid electrolyte layer can be the same or different.

[0453] In some embodiments of this application, the solid electrolyte layer includes at least a first electrolyte layer. The definition of the first electrolyte layer can be found in the first aspect of this application. In some embodiments, the solid electrolyte layer may also optionally include a second electrolyte layer. The types of solid electrolytes in the first electrolyte layer and the second electrolyte layer may be the same or different.

[0454] In some embodiments of this application, the first electrolyte layer includes a sulfide-based solid electrolyte. The first electrolyte layer may also include solid electrolytes known in the art and suitable for solid-state batteries. In the first electrolyte layer, these solid electrolytes may be used alone or in combination of two or more. In some embodiments, the first electrolyte layer may also include one or more of the following materials: halide-based solid electrolytes, oxide-based solid electrolytes, polymer-based solid electrolytes, etc.

[0455] In this application, "sulfide solid electrolyte" and "sulfide solid electrolyte" have the same meaning and can be used interchangeably. A sulfide solid electrolyte can be a sulfide or any suitable modified form of a sulfide. Sulfide solid electrolytes can be modified using conventional methods in the art or methods suitable for the solid-state batteries of this application to obtain new sulfide solid electrolytes.

[0456] As a non-limiting example, in the second electrolyte layer, the solid electrolyte includes one or more of sulfide solid electrolytes, halide solid electrolytes, oxide solid electrolytes, and polymer solid electrolytes. In some non-limiting examples, the solid electrolyte in the second electrolyte layer may include, but is not limited to, one or more of oxide solid electrolytes, sulfide solid electrolytes, and halide solid electrolytes.

[0457] Non-limiting examples of oxide solid electrolytes may include LISICON-type oxide electrolytes (such as γ-Li3PO4, etc.) and NASICON-type oxide electrolytes (such as Li...). 1+x Al x Ge 2-x (PO4)3,Li 1+x Al x Ti 2-x (PO4)3, etc., 0≤x≤1), Garnet type (such as Li7La3Zr2O) 12 (etc.), perovskite-type oxide electrolytes (such as Li, etc.) 3x La 2 / 3-x One or more of TiO3, etc. (0≤x≤0.5), etc.

[0458] Non-limiting examples of sulfide solid electrolytes may include Li 10 GeP2S 12 Li₂S-P₂S₅, Argyrodite type (such as Li₆PS₅Cl, Li 5.5 PS 5.5 Cl 1.5 One or more of the following: etc.

[0459] Non-limiting examples of halide solid electrolytes may include one or more of Li3InCl6, Li3YCl6, Li3ScCl6, Li3ErCl6, Li2ZrCl6, etc.

[0460] The following are some other descriptions of the negative electrode layer.

[0461] In some implementations, the negative electrode layer may be provided by an electrolyte negative electrode sheet as described in the context of this application.

[0462] In other embodiments, the negative electrode layer may be formed based on a solid electrolyte membrane or provided by a pre-fabricated negative electrode sheet, which may be a negative electrode sheet that is available in the art for use in solid-state batteries.

[0463] The negative electrode sheet can be prepared by dry or wet methods. For example, it can be formed into a film by dry pressing. Alternatively, it can be formed into a film by wet coating.

[0464] In this application, unless otherwise specified, the negative electrode layer includes at least a negative electrode active material layer.

[0465] Unless otherwise stated in this application, the negative electrode sheet includes at least a negative electrode active material layer.

[0466] Unless otherwise stated in this application, the negative electrode active material layer includes at least negative electrode active particles.

[0467] Without limitation, the negative electrode active material layer may include a solid electrolyte. The solid electrolyte in the negative electrode active material layer may be referred to as "negative electrode electrolyte particles".

[0468] In this application, unless otherwise specified, "negative electrode electrolyte particles" refers to a solid electrolyte that can be used in the negative electrode layer. Negative electrode electrolyte particles can enhance the ion conductivity of the negative electrode layer, reduce interfacial impedance, and promote the charge transfer efficiency and full release of the capacity of the negative electrode active material with the external environment. The type of negative electrode electrolyte particles can be the same as or different from those in the solid electrolyte layer.

[0469] In this application, unless otherwise stated, "negative electrode active particles" refers to particles containing negative electrode active substances that have the ability to reversibly insert and extract active ions.

[0470] Without limitation, the weight percentage of negative electrode active particles or negative electrode active materials in the negative electrode active material layer can be ≥80wt%, and more preferably ≥90wt%.

[0471] Non-limiting, the weight percentage of the negative electrode electrolyte particles in the negative electrode active material layer can be 0 to 30 wt%, preferably 0.1 wt% to 30 wt%, and further preferably 5 wt% to 20 wt%.

[0472] In some embodiments, the negative electrode active particles or negative electrode active material are lithium indium alloys (InLi alloys).

[0473] In some implementations, the negative electrode layer or negative electrode sheet is an InLi alloy electrode sheet.

[0474] In some embodiments, the negative electrode active material may also be a negative electrode active material known in the art for use in solid-state batteries. As a non-limiting example, the negative electrode active material may include one or more of the following materials: elemental silicon, elemental tin, silicon-carbon composites, silicon suboxide, graphite, and metallic lithium. However, this application is not limited to these materials or substances, and other conventional materials that can be used as battery negative electrode active materials may also be used. These negative electrode active materials may be used alone or in combination of two or more.

[0475] In some embodiments, the negative electrode active material layer comprises a silicon-based material. Without limitation, the silicon-based material may include, but is not limited to, one or more of elemental silicon, silicon-carbon composites, silicon oxides, etc.

[0476] In some embodiments, the negative electrode sheet may include a negative electrode current collector and a negative electrode active material layer disposed on at least one surface of the negative electrode current collector, the negative electrode active material layer comprising a negative electrode active substance. As a non-limiting example, the negative electrode current collector has two surfaces opposite to each other in its own thickness direction, and the negative electrode active material layer is disposed on either or both of the two opposite surfaces of the negative electrode current collector. In some embodiments, the negative electrode current collector may be a metal foil or a composite current collector. For example, copper foil may be used as the metal foil. In the negative electrode current collector, the composite current collector may include a polymer material base layer and a metal layer formed on at least one surface of the polymer material base layer. In the negative electrode current collector, the composite current collector may be formed by forming a metal material on the polymer material base layer. Non-limiting examples of the metal material in the negative electrode current collector may include one or more of copper, copper alloys, nickel, nickel alloys, titanium, titanium alloys, silver, and silver alloys. In the negative electrode current collector, non-limiting examples of the polymeric material substrate may include one or more of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.

[0477] In some embodiments, the negative electrode active material layer optionally includes a conductive agent (which may be referred to as a negative electrode conductive agent). Non-limitingly, the negative electrode conductive agent may include one or more of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers. Non-limitingly, the weight percentage of the negative electrode conductive agent in the negative electrode active material layer may be 0–15 wt%, more preferably 0–10 wt%, and even more preferably 0–5 wt%.

[0478] In some embodiments, the negative electrode active material layer optionally includes a binder (denoted as negative electrode binder). As a non-limiting example, the negative electrode binder may include one or more of polyvinylidene fluoride (PVDF), styrene-butadiene rubber (SBR), polyacrylic acid (PAA), sodium polyacrylate (PAAS), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium alginate (SA), polymethacrylic acid (PMAA), and carboxymethyl chitosan (CMCS). Non-limitingly, the weight percentage of the negative electrode binder in the negative electrode active material layer may be 0–10 wt%, more preferably 0–5 wt%, even more preferably 1 wt%–5 wt%, and even more preferably 1 wt%–3 wt%.

[0479] In some embodiments, the negative electrode active material layer may optionally include other additives, such as thickeners (e.g., sodium carboxymethyl cellulose (CMC-Na)). The weight percentage of the other additives in the negative electrode active material layer may be 0–15 wt%, more preferably 0–10 wt%, even more preferably 0–5 wt%, even more preferably 0–3 wt%, and even more preferably 0–2 wt%.

[0480] In some embodiments, the negative electrode sheet can be prepared by dispersing the components used to prepare the negative electrode sheet, such as negative electrode active particles, negative electrode conductive agent, negative electrode binder, and any other components, in a solvent (non-limiting examples of solvents include p-xylene, N-methyl-2-pyrrolidone (NMP), etc.), to form a negative electrode slurry. Further, the negative electrode slurry is coated onto at least one surface of the negative electrode current collector, and after drying, cold pressing, and other processes, the negative electrode sheet is obtained. Cold pressing can be performed using a cold rolling mill. The surface of the negative electrode current collector coated with the negative electrode slurry can be a single surface of the negative electrode current collector or both surfaces of the negative electrode current collector. The solid content of the negative electrode slurry can be 30wt% to 70wt%, optionally 40wt% to 60wt%. The viscosity of the negative electrode slurry at room temperature can be adjusted to 2000 mPa·s to 10000 mPa·s, optionally 3000 mPa·s to 10000 mPa·s. When coating the negative electrode slurry, the coating density per unit area (after deducting solvent) on a dry weight basis, based on the amount coated on one side of the negative electrode current collector, can be 1.3 mg / cm³. 2~22mg / cm 2 However, this is not the only possibility. The compaction density of the negative electrode sheet can be 1.0 g / cm³. 3 ~2.0g / cm 3 1.0g / cm³ is an optional value. 3 ~1.8g / cm 3 .

[0481] The following is a description of the positive electrode layer.

[0482] The positive electrode layer can be formed based on a solid electrolyte membrane or provided by a pre-fabricated positive electrode sheet, which can be a positive electrode sheet that is available in the art for use in solid-state batteries.

[0483] Positive electrode sheets can be prepared using dry or wet methods. For example, they can be dry-pressed into films. Alternatively, they can be wet-coated and dried to form films.

[0484] In some embodiments, the positive electrode layer includes a positive electrode current collector and a positive electrode active material layer disposed on at least one surface of the positive electrode current collector.

[0485] Unless otherwise stated, the positive electrode layer in this application includes at least a positive electrode active material layer.

[0486] Unless otherwise stated in this application, the positive electrode sheet includes at least a positive active material layer.

[0487] In this application, unless otherwise specified, the positive electrode active material layer includes at least positive electrode active particles, and usually also includes positive electrode electrolyte particles.

[0488] In this application, unless otherwise specified, "positive electrode active particles" refers to particles containing positive electrode active substances that have the ability to reversibly extract and insert active ions.

[0489] In this application, unless otherwise specified, "positive electrode electrolyte particles" refers to solid electrolytes that can be used in the positive electrode layer. Positive electrode electrolyte particles can enhance the ion conductivity of the positive electrode layer, reduce interfacial impedance, and promote the charge transfer efficiency and full release of the capacity of the positive electrode active material with the external environment.

[0490] In some embodiments, the positive electrode active material may be a known positive electrode active material for batteries. As a non-limiting example, the positive electrode active material may include one or more of the following materials: lithium-containing phosphates with an olivine structure, lithium transition metal oxides, and their respective modified compounds. However, this application is not limited to these materials, and other conventional materials that can be used as positive electrode active materials for batteries may also be used. These positive electrode active materials may be used alone or in combination of two or more. Examples of lithium transition metal oxides include, but are not limited to, one or more of lithium cobalt oxide, lithium nickel oxide, lithium manganese oxide, lithium nickel cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide, lithium nickel cobalt aluminum oxide, and their modified compounds. Non-limiting examples of lithium-containing phosphates with an olivine structure include, but are not limited to, one or more of lithium iron phosphate, lithium iron phosphate and carbon composites, lithium manganese phosphate, lithium manganese phosphate and carbon composites, lithium iron manganese phosphate, and lithium manganese iron phosphate and carbon composites. Non-limiting examples of lithium cobalt oxides may include LiCoO2; non-limiting examples of lithium nickel oxides may include LiNiO2; non-limiting examples of lithium manganese oxides may include LiMnO2, LiMn2O4, etc.; non-limiting examples of lithium nickel cobalt manganese oxides may include LiNi 1 / 3 Co 1 / 3 Mn 1 / 3 O2 (also known as NCM) 333 LiNi 0.5 Co 0.2 Mn 0.3 O2 (also known as NCM) 523 LiNi 0.5 Co 0.25 Mn 0.25 O2 (also known as NCM) 211 LiNi 0.6 Co 0.2 Mn 0.2 O2 (also known as NCM) 622 LiNi 0.8 Co 0.1 Mn 0.1 O2 (also known as NCM) 811 Examples of lithium nickel cobalt aluminum oxides include LiNi, etc. 0.80 Co 0.15 Al 0.05 O2. Examples of lithium iron phosphate include LiFePO4 (also known as LFP). Examples of lithium manganese phosphate include LiMnPO4.

[0491] Understandably, lithium (Li) is intercalated and deintercalated during the charging and discharging process of a battery, resulting in different Li content in the positive electrode layer or positive electrode sheet when the battery is discharged to different states. In the exemplary description of the positive electrode active material in this application, unless otherwise specified, the Li content can be the initial state of the material or a non-initial state after charge-discharge cycles. When the positive electrode active material is applied to the positive electrode in a battery system, the Li content in the positive electrode active material at the positive electrode will usually change after charge-discharge cycles. The Li content can be measured in atomic molar content, but is not limited to this. Regarding "Li content is the initial state of the material," the initial state of the material refers to the state before it is made into the positive electrode active material layer. It is understood that new materials or substances obtained by appropriate modification based on the listed positive electrode active materials are also within the scope of positive electrode active materials. The aforementioned appropriate modification refers to an acceptable modification method for the positive electrode active material, and non-limiting examples include coating modification.

[0492] In the exemplary description of the positive electrode active material in this application, the oxygen (O) content is only a theoretical value. Lattice oxygen release will cause changes in the atomic molar content of oxygen, and the actual O content will fluctuate. The O content can be measured using atomic molar content, but is not limited to this.

[0493] Non-limiting, the weight percentage of positive electrode active particles or positive electrode active materials in the positive electrode active material layer can be ≥70wt%, further ≥80wt%, even further ≥90wt%, and can also be 70wt% to 99wt%, optionally 80wt% to 95wt%.

[0494] Non-limiting, the weight percentage of positive electrode electrolyte particles in the positive electrode active material layer can be 0.1 wt% to 30 wt%, and optionally 5 wt% to 20 wt%.

[0495] In some embodiments, the positive electrode active material layer includes positive electrode electrolyte particles. Non-limitingly, the weight percentage of the positive electrode electrolyte particles in the positive electrode active material layer can be from 0.1 wt% to 30 wt%, optionally from 5 wt% to 20 wt%.

[0496] In some embodiments, the positive electrode active material layer includes positive electrode active particles and positive electrode electrolyte particles.

[0497] In some embodiments, the positive electrode active material layer includes a conductive agent (which may be referred to as a positive electrode conductive agent). As a non-limiting example, the positive electrode conductive agent may be a carbon conductive agent. Non-limitingly, the carbon conductive agent may include one or more of superconducting carbon, acetylene black, carbon black, Ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers. In some embodiments, the positive electrode conductive agent may include, but is not limited to, one or more of SP, KS-6, acetylene black, branched Ketjen black ECP, SFG-6, vapor-grown carbon fibers (VGCF), carbon nanotubes (CNTs), and graphene. Non-limitingly, the weight percentage of the positive electrode conductive agent in the positive electrode active material layer may be 0–10 wt%, more further 0–8 wt%, even further 0–5 wt%, and even further 0.1 wt%–3 wt%. When the positive electrode material is prepared into a positive electrode active material layer using a dry method, the positive electrode conductive agent can be incorporated into the positive electrode material, which can improve the conductivity of the positive electrode active material layer.

[0498] In some embodiments, the positive electrode active material layer optionally includes a binder (which may be referred to as a positive electrode binder). As a non-limiting example, the positive electrode binder may include one or more of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), a terpolymer of PVDF-tetrafluoroethylene-propylene, a terpolymer of PVDF-hexafluoropropylene-tetrafluoroethylene, a tetrafluoroethylene-hexafluoropropylene copolymer, and fluorinated acrylate resins. The aforementioned non-limiting examples of positive electrode binders are all organic binders and belong to organic components. Typically, the weight percentage of the positive electrode binder in the positive electrode active material layer can be 0–10 wt%, more commonly 0–8 wt%, even more commonly 0.1 wt%–5 wt%, and even more commonly 1 wt%–5 wt%. When the positive electrode material is formulated into a positive electrode slurry using a wet process and then the positive electrode active material layer is prepared, the positive electrode binder can be placed in the positive electrode slurry, which can assist in film formation and also promote the formation of a good electrical contact network between the active particles in the positive electrode active material layer.

[0499] Non-limiting, the positive electrode active material layer may include positive electrode active particles, positive electrode electrolyte particles, positive electrode conductive agent, and positive electrode binder. The types and contents of each component can be found in the context of this application.

[0500] As a non-limiting example, the positive current collector has two surfaces that are opposite to each other in its own thickness direction, and the positive active material layer is disposed on either or both of the two opposite surfaces of the positive current collector.

[0501] In some embodiments, the positive electrode current collector may be a metal foil or a composite current collector. For example, aluminum foil may be used as the metal foil. In the positive electrode current collector, the composite current collector may include a polymer material substrate and a metal layer formed on at least one surface of the polymer material substrate. In the positive electrode current collector, the composite current collector may be obtained by forming a metal material on the polymer material substrate. Non-limiting examples of the metal material in the positive electrode current collector may include at least one of aluminum, aluminum alloy, nickel, nickel alloy, titanium, titanium alloy, silver, and silver alloy. Non-limiting examples of the polymer material substrate in the positive electrode current collector may include one or more of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), and polyethylene (PE).

[0502] In some embodiments, the positive electrode sheet can be prepared by: dry mixing the components used to prepare the positive electrode sheet, such as positive electrode active particles, positive electrode electrolyte particles, positive electrode conductive agent, positive electrode binder, and any other components; then heating and pressurizing the mixed material to knead it into a clump; hot rolling pressing to form a self-supporting positive electrode sheet; and hot rolling bonding the self-supporting positive electrode sheet with a positive electrode current collector, wherein the self-supporting positive electrode sheet can be bonded to at least one side (single or double sides) of the positive electrode current collector to obtain the positive electrode sheet. Non-limitingly, a dual planetary mixer can be used for dry mixing. Non-limitingly, a kneading and pressing process can be performed using a Banbury mixer. Non-limitingly, the temperature for hot rolling pressing can be 75°C to 85°C, and further, such as 78°C, 80°C, 82°C, etc. The method of assembling solid-state batteries using positive electrode sheets is suitable for industrial mass production.

[0503] In some embodiments, the positive electrode sheet can be prepared by dispersing the components used to prepare the positive electrode sheet, such as positive electrode active particles, positive electrode electrolyte particles, positive electrode conductive agent, positive electrode binder, and any other components, in an organic solvent to form a positive electrode slurry. Further, the positive electrode slurry is coated onto at least one surface of the positive electrode current collector, and after drying, cold pressing, and other processes, the positive electrode sheet is obtained. Cold pressing can be performed using a cold rolling mill. Non-limitingly, the organic solvent in the positive electrode slurry can include one or more of p-xylene, trimethylbenzene, butyl butyrate, heptane, etc., and more specifically, p-xylene. The surface of the positive electrode current collector coated with the positive electrode slurry can be a single surface of the positive electrode current collector or both surfaces of the positive electrode current collector. The solid content of the positive electrode slurry can be 40 wt% to 80 wt%. The viscosity of the positive electrode slurry at room temperature can be adjusted to 5000 mPa·s to 25000 mPa·s. When coating the positive electrode slurry, the coating density per unit area, measured by dry weight (excluding solvent), can be 15 mg / cm³, based on the amount coated on one side of the positive electrode current collector. 2 ~35mg / cm2 However, this is not the only possibility. The compaction density of the positive electrode sheet can be 2.0 g / cm³. 3 ~3.6g / cm 3 2.3g / cm³ is an option. 3 ~3.5g / cm 3 .

[0504] In some embodiments of the fourth aspect of this application, a method for preparing a solid electrolyte membrane is provided, comprising the following steps:

[0505] An electrolyte slurry comprising a first solid electrolyte, a first binder, and an organic solvent is prepared; wherein the first solid electrolyte comprises a sulfide solid electrolyte, and the first binder comprises a first binder;

[0506] The electrolyte slurry is coated onto the film-forming substrate and dried to form a solid electrolyte membrane on the film-forming substrate.

[0507] In some embodiments, the first adhesive satisfies one or both of the following characteristics:

[0508] (t1) The water absorption rate of the first adhesive is less than or equal to 0.1%;

[0509] (t2) The first binder includes a cyclic olefin / chain olefin copolymer, wherein the monomer units of the cyclic olefin / chain olefin copolymer include cyclic olefin monomer units and chain olefin monomer units, and the chain backbone of the cyclic olefin / chain olefin copolymer includes a cyclic structure provided by the cyclic olefin monomer units.

[0510] In some embodiments, the solid electrolyte membrane is prepared by a method for preparing a solid electrolyte membrane, as described in the first aspect of this application.

[0511] In some embodiments, the first electrolyte layer is as defined in the first aspect of this application.

[0512] The prepared solid electrolyte membrane has the advantages of the aforementioned solid electrolyte membrane.

[0513] In some embodiments, the water absorption rate of the first adhesive is ≤0.1%.

[0514] In some embodiments, the electrolyte slurry may optionally include a second binder, the definition of which can be found in the context of this application. For example, the second binder has a water absorption rate of ≥0.5%.

[0515] In a fifth aspect of this application, a method for preparing a solid-state battery is provided, comprising the following steps:

[0516] An electrolyte electrode sheet is prepared; wherein the electrolyte electrode sheet includes a first electrode layer and a first electrolyte layer located on at least one side of the first electrode layer; wherein the first electrolyte layer includes a first solid electrolyte and a first binder layer, the first solid electrolyte including a sulfide solid electrolyte, and the first binder layer including a first binder.

[0517] A second electrode layer is formed on the side of the first electrolyte layer away from the first electrode layer.

[0518] In some embodiments, the first adhesive satisfies one or both of the following characteristics:

[0519] (t1) The water absorption rate of the first adhesive is less than or equal to 0.1%;

[0520] (t2) The first binder includes a cyclic olefin / chain olefin copolymer, wherein the monomer units of the cyclic olefin / chain olefin copolymer include cyclic olefin monomer units and chain olefin monomer units, and the chain backbone of the cyclic olefin / chain olefin copolymer includes a cyclic structure provided by the cyclic olefin monomer units.

[0521] In some embodiments, the electrolyte electrode is as defined in the second aspect of this application, or the first electrolyte layer is as defined in the first aspect of this application.

[0522] In some embodiments, the electrolyte slurry further includes a second binder with a water absorption rate ≥0.5%.

[0523] The solid-state battery prepared includes the advantages of the aforementioned solid-state batteries, which will not be repeated here.

[0524] In some embodiments, the first electrolyte layer is formed on at least one side of the first electrode layer by coating and drying an electrolyte slurry; wherein the electrolyte slurry includes a first solid electrolyte, a first binder, and an organic solvent. When the first electrolyte layer further includes a second binder, the electrolyte slurry also includes a second binder.

[0525] In some embodiments, the electrolyte electrode sheet can be prepared by a method including the following steps: coating an electrolyte slurry onto at least one surface of a first electrode sheet and drying it to obtain the electrolyte electrode sheet; wherein the first electrode sheet forms a first electrode layer and the dried electrolyte slurry forms a first electrolyte layer.

[0526] When forming the first electrolyte layer using a wet process with an electrolyte slurry, introducing a first binder with low water absorption can reduce the water absorption of the electrolyte slurry, decrease the probability of contact reaction between the sulfide solid electrolyte and water, and reduce or inhibit the decomposition of the sulfide solid electrolyte. This reduces the release of hydrogen sulfide and the stability of the sulfide solid electrolyte during the preparation of the electrolyte electrode, and also improves the material stability of the electrolyte electrode, which is beneficial to improving the quality stability of the solid-state battery obtained in further preparation. Furthermore, the release of hydrogen sulfide from the solid-state battery prepared based on this electrolyte electrode in a water-containing environment (such as air) can be correspondingly reduced.

[0527] In some embodiments, the electrolyte electrode is an electrolyte negative electrode, and the solid-state battery preparation method includes the following steps:

[0528] S100: An electrolyte slurry is coated onto at least one side surface of a negative electrode sheet and dried to prepare an electrolyte negative electrode sheet; wherein, the negative electrode sheet forms a negative electrode layer, and the dried electrolyte slurry forms a first electrolyte layer;

[0529] S210: A second electrolyte layer and a positive electrode layer are formed sequentially on the side of the first electrolyte layer away from the negative electrode layer.

[0530] For the preparation method of the negative electrode sheet, please refer to the context of this application.

[0531] In some embodiments, the dielectric constant ε of the organic solvent in the electrolyte slurry satisfies: ε≤6.5.

[0532] In this application, unless otherwise specified, the dielectric constant of organic solvents can be tested using the frequency method, which determines the dielectric constant based on the polarization phenomenon of solvent molecules under an alternating electric field. The testing instrument includes a frequency-adjustable AC power supply and a capacitance meter. The test can be performed as follows: the organic solvent to be tested is injected into the capacitance meter until it is fully filled; the frequency f of the AC power supply is set and connected to the capacitance meter; the capacitance value C at different frequencies is measured and recorded; the dielectric constant ε is calculated according to the following formula. Where K is the electrostatic constant, K = 9.0 × 10⁻⁶ 9 N·m 2 / C 2 C is the capacitance; d is the distance between the two plates; S is the area of ​​the two plates facing each other; the capacitance C can be calculated using the following formula: Where ω is the angular velocity, Z” is the imaginary part of the complex impedance (or the capacitive reactance); ω=2πf.

[0533] In some embodiments, the organic solvent in the electrolyte slurry includes organic solvent A, wherein the dielectric constant ε of organic solvent A is ≤ 6.5. Optionally, organic solvent A includes one or more of a low-polarity solvent and a non-polar solvent.

[0534] In some embodiments, the organic solvent in the electrolyte slurry includes one or more organic solvents with a dielectric constant less than or equal to 6.5.

[0535] In some embodiments, the organic solvent in the electrolyte slurry includes one or more of a low-polarity solvent and a non-polar solvent; non-limitingly, the dielectric constant ε1 of the low-polarity solvent satisfies: 2.6 < ε1 ≤ 6.5; and the dielectric constant ε2 of the non-polar solvent satisfies: ε2 ≤ 2.6.

[0536] In some embodiments, the organic solvent in the electrolyte slurry includes substituted benzene, wherein the phenyl group in the substituted benzene is replaced by one or more substituents selected from the substituent group G, which includes methyl, chlorine, and methoxy groups.

[0537] In some embodiments, the organic solvent in the electrolyte slurry may include, but is not limited to, one or more of toluene, xylene, butyl butyrate, octyl butyrate, trimethylbenzene, toluene, chlorobenzene, dimethyl carbonate, ethyl acetate, n-hexane, anisole, dibromomethane, triethyl phosphate, isopropyl ether, and benzyl acetate. Butyrate may include one or more of n-butyl butyrate, isobutyl isobutyrate, etc. Further, the organic solvent in the electrolyte slurry may include one or more of p-xylene, pseudotrimethylbenzene, toluene, butyl butyrate (examples of butyl butyrate include one or more of n-butyl butyrate, isobutyl isobutyrate, etc.), and octyl butyrate.

[0538] In some embodiments, the organic solvent in the electrolyte slurry is 30 wt% to 90 wt%, optionally 40 wt% to 70 wt%, or any of the following percentages or a range selected from any two of the following percentages: 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 70 wt%, 80 wt%, 90 wt%, etc.

[0539] In some embodiments, the organic solvent with a dielectric constant less than or equal to 6.5 constitutes 30 wt% to 90 wt% of the electrolyte slurry, optionally 40 wt% to 70 wt%, or any of the following percentages or a range selected from any two of the following percentages: 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, 70 wt%, 80 wt%, 90 wt%, etc. In some embodiments, the organic solvent satisfies one or more of the following characteristics (any numerical parameter of the following characteristics may also be selected from any suitable value or range in the context):

[0540] Organic solvents include one or more of low-polarity solvents and non-polar solvents; wherein, the dielectric constant ε1 of the low-polarity solvent satisfies: 2.6 < ε1 ≤ 6.5; and the dielectric constant ε2 of the non-polar solvent satisfies: ε2 ≤ 2.6.

[0541] The organic solvent includes substituted benzene, wherein the phenyl group in the substituted benzene is replaced by one or more substituents selected from the substituent group G, which includes: methyl, chlorine atom and methoxy;

[0542] The organic solvent has a weight percentage of 50 wt% to 100 wt%, and can be optionally 70 wt% to 100 wt%.

[0543] The organic solvents include one or more of toluene, xylene, butyl butyrate, octyl butyrate, trimethylbenzene, toluene, chlorobenzene, dimethyl carbonate, ethyl acetate, n-hexane, anisole, dibromomethane, triethyl phosphate, isopropyl ether, and benzyl acetate; optionally, the organic solvents include one or more of p-xylene, pseudotrimethylbenzene, toluene, butyl butyrate (examples of butyl butyrate include one or more of n-butyl butyrate, isobutyl isobutyrate, etc.) and octyl butyrate;

[0544] The organic solvent in the electrolyte slurry is 30 wt% to 90 wt%, and optionally 40 wt% to 70 wt%.

[0545] For electrolyte slurry systems containing the aforementioned organic solvents, selecting low-polarity or non-polar solvents can reduce side reactions with highly reactive sulfide solid electrolytes.

[0546] In some embodiments, the electrolyte electrode is the electrolyte electrode described in the second aspect of this application, and the first electrode layer includes a corresponding electrode body.

[0547] In some embodiments, the solid-state battery prepared is the solid-state battery described in the third aspect of this application.

[0548] In a sixth aspect of this application, an electrical device is provided, comprising at least one of the following: a solid electrolyte membrane as described in the first aspect of this application, an electrolyte electrode as described in the second aspect of this application, a solid-state battery as described in the third aspect of this application, a solid electrolyte membrane prepared by the method for preparing the solid electrolyte membrane as described in the fourth aspect of this application, and a solid-state battery prepared by the method for preparing the solid electrolyte membrane as described in the fifth aspect of this application.

[0549] In some of these embodiments, the power supply device includes a solid-state battery according to any of the embodiments provided in this application.

[0550] In a non-limiting sense, solid-state batteries can be used as a power source for electrical devices or as an energy storage unit for electrical devices. Electrical devices can include, but are not limited to, mobile devices, electric vehicles, electric trains, ships and satellites, energy storage systems, etc. Mobile devices can be, for example, mobile phones, laptops, etc.; electric vehicles can be, for example, pure electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf carts, electric trucks, electric motorcycles, power tools, etc., but are not limited to these. This electrical device can also be applied to military equipment, aerospace, and other fields, and can also be applied to energy storage power systems such as hydroelectric, thermal, wind, and solar power plants.

[0551] As an electrical device, solid-state batteries can be selected based on its usage requirements.

[0552] Figure 16 shows an example of an electrical device 6. This electrical device is a pure electric vehicle, a hybrid electric vehicle, or a plug-in hybrid electric vehicle, etc. To meet the high power and high energy density requirements of this electrical device for solid-state batteries, a battery pack or battery device can be used.

[0553] Another example device could be a mobile phone, tablet, or laptop. These devices typically require a thin and light design and can use solid-state batteries as their power source.

[0554] The cyclic olefin / chain olefin copolymers involved in this application can be prepared using existing copolymerization methods in the field of polymer synthesis, based on the types and proportions of cyclic olefin monomer units and chain olefin monomer units. Appropriate structural monomers can be selected according to the types of cyclic olefin monomer units and chain olefin monomer units, and the feed ratio of corresponding monomer units can be selected according to the molar ratio of different monomer units in the designed structure of the cyclic olefin / chain olefin copolymer. The copolymers are obtained through addition copolymerization under the action of a catalyst. By controlling one or more parameters of the reaction system, such as the type and amount of catalyst, reaction temperature and time, and optional reaction pressure, parameters or characteristics such as the molecular weight of the copolymer, the proportion of cyclic structures in the chain backbone, the rigidity of the copolymer, and water absorption can be adjusted. By controlling the addition copolymerization reaction between the cyclic olefin monomer and the monomer containing α-olefin groups, the cyclic structure of the cyclic olefin monomer can be retained in the main chain of the copolymer, so that the chain backbone of the cyclic olefin / chain olefin copolymer includes the cyclic structure provided by the cyclic olefin monomer units. Those skilled in the art can select a suitable copolymerization method according to the structural requirements of the cyclic olefin / chain olefin copolymer.

[0555] For those skilled in the art, given the selected monomer unit types and molar ratios of the cyclic olefin / chain olefin copolymer, appropriate monomer raw material types and amounts, catalyst types and amounts, and suitable reaction conditions can be chosen by combining relevant synthetic techniques to obtain the designed structure. The copolymer product can be characterized and structurally identified using known methods in relevant synthetic fields (including but not limited to conventional methods). For example, one or more of the following methods can be used, but are not limited to: Fourier transform infrared (FT-IR) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy (NMR)... 1 H NMR (1H NMR) method, carbon nuclear magnetic resonance (NMR) spectroscopy 13 Methods include C NMR, gel permeation chromatography (GPC), ultraviolet-visible spectroscopy (UV-vis), thermogravimetric analysis (TGA) or micro-quotient thermogravimetric analysis (DTG), differential scanning calorimetry (DSC), dynamic thermomechanical analysis (DMA), and viscosity testing.

[0556] The following describes some embodiments of this application. The embodiments described below are exemplary and are only used to explain this application, and should not be construed as limiting this application. Where the technology or conditions are not specified in the embodiments, they are performed according to the description above, or according to the technology or conditions described in the literature in this field, or according to the product instructions. Reagents or instruments whose manufacturers are not specified are all conventional products that can be obtained commercially, or can be synthesized from commercially available products using conventional methods.

[0557] It should be noted that the following embodiments and examples use all-solid-state batteries as non-limiting examples of solid-state batteries.

[0558] Taking the preparation of addition-type cyclic olefin / chain olefin copolymers (norbornene-ethylene copolymers) using cyclic olefin monomers as norbornene and monomers containing α-alkenyl groups as monomers as examples, their general structural formula can be represented as follows: m and n are integers, and the m:n ratio can be controlled by adjusting the feed ratio of the two monomers. A high-pressure stainless steel reactor is used, and the copolymerization reaction is carried out under anhydrous and oxygen-free conditions and an argon atmosphere. α-Diimine nickel catalyst can be selected as the main catalyst, with methylaluminoxane (MAO) as the co-catalyst, and chlorobenzene as the reaction solvent. The aluminum-nickel ratio of the co-catalyst to the main catalyst is controlled at 1200–1500, the reaction pressure at 0.4 MPa–0.6 MPa, the reaction temperature at 60℃–80℃, and the reaction time at 0.5–2 h. At the end of the reaction, the polymerization reaction can be terminated by acidifying with ethanol.

[0559] The structure of the α-diimine nickel catalyst is as follows: Wherein, R1 is -PhCH2OH, Ph is phenylene, and R2 isopropyl.

[0560] The norbornene-ethylene copolymer used in the following examples was copolymerized using the following method: Under argon protection, the reaction solvent, norbornene solution, and co-catalyst were added sequentially, stirred for 5 minutes to mix, then the main catalyst solution was added, ethylene was rapidly introduced, and the pressure inside the reactor was controlled to reach a suitable reaction pressure. Stirring was started, and the reaction was allowed to proceed for a certain time. At the end of the reaction, the ethylene supply was stopped, the temperature was lowered, the pressure was released, and the reaction mixture was added to 10% (v / v) acidified ethanol (acidified with hydrochloric acid). Stirring was used to terminate the polymerization reaction. The mixture was filtered, the solid phase was collected, and washed repeatedly with distilled water and anhydrous ethanol (at least 3 times, such as 3-5 times). The mixture was then filtered again and dried in an oven at 60°C. The amount of α-diimine nickel catalyst was controlled to ensure that the Ni content in the reaction solution was 5 μmol, the aluminum-nickel ratio was 1500, the reaction pressure was 0.5 MPa, the reaction temperature was 70°C, and the reaction time was approximately 1.5-2 hours. The content of norbornene units in the copolymer can be controlled by adjusting the amount of norbornene added; increasing the amount of norbornene added can increase the content of norbornene units.

[0561] Characterization methods for norbornene-ethylene copolymers: based on Fourier transform infrared (FT-IR) spectroscopy and carbon nuclear magnetic resonance (CMR) spectroscopy. 13 The structure was confirmed by 12C NMR. Analysis of the 940 cm⁻¹ FT-IR spectrum was performed. -1 Does the absorption peak of the bicyclic [2.2.1]heptane ring of the addition polymer appear nearby, at 1467 cm⁻¹? -1 Does the CH scissor vibration absorption peak of methylene CH2 appear nearby, at 966 cm⁻¹? - and 736cm -1Whether there are no transC=C out-of-plane rocking vibration absorption peaks and cisC=C out-of-plane rocking vibration absorption peaks in the vicinity of the ring-opening polymer, in addition, the following characteristic peak can be used for analysis: 2946 cm⁻¹ -1 2869cm -1 Does the saturated CH symmetric or asymmetric stretching vibration absorption peak appear nearby at 2353 cm⁻¹? - 1 Are characteristic absorption peaks of CO2 in the air present nearby? Based on... 13 The C1 / C1 NMR spectrum was analyzed to determine whether the relevant characteristic peaks in equation (I) appeared in the chemical shift range of 10-60 ppm: C2 / C3 chemical shifts were 44.7-57.2 ppm, C1 / C4 chemical shifts were 36.8-44.1 ppm, and C7 chemical shifts were 32.9-36.5 ppm; C5 / C6 and C1 / C1 / C2 / C3 chemical shifts were 32.9-36.5 ppm. α / C β The chemical shift is 26.8-32.8 ppm. Further, according to... 13 The m:n ratio is calculated by the integral area ratio of each characteristic peak in the C NMR spectrum. The molecular weight information of the copolymer, including weight-average molecular weight and number-average molecular weight, is confirmed by GPC testing. Based on this, the values ​​of m and n, and the m:n ratio, are estimated.

[0562] The FT-IR test used the potassium bromide pellet method, with a scanning range of 4000–400 cm⁻¹. -1 . 13 C10 NMR was performed using deuterated o-dichlorobenzene as the solvent at a temperature of 120°C. GPC was performed using 1,2,4-trichlorobenzene as the solvent at a temperature of 140°C.

[0563] The molar fraction f1 (mol%) of the norbornene monomer unit in the cyclic olefin / chain olefin copolymer of formula (I) obtained by copolymerization of norbornene and ethylene can be calculated using the following formula: f1 (mol%) = [(A+B+2C) / 3D]×100%. Where A represents the integral area of ​​C1 / C4 of the copolymer in the carbon NMR spectrum, B represents the integral area of ​​C2 / C3 of the copolymer in the carbon NMR spectrum, C represents the integral area of ​​C7 of the copolymer in the carbon NMR spectrum, and D represents the carbon atoms of C5 / C6 and the methylene group of the ethylene unit in the copolymer. α / C β The integrated area in the carbon NMR spectrum.

[0564] In the following examples, addition-type cyclic olefin / chain olefin copolymers were prepared using norbornene and monomers containing α-alkenyl groups via the following synthetic methods:

[0565] The water absorption rate of cyclic olefin / chain olefin copolymer materials was tested using the following water absorption rate test method.

[0566] In the following examples, the water absorption rate of different adhesive materials was tested according to the national standard GB / T 1037 using the specific gravity method. The steps are as follows:

[0567] (1) The test temperature is 23℃. Weigh the absorbent paper and record the actual mass M1. Then put it in the drying room. After standing for at least 2 hours, weigh the adhesive material and record it as M2.

[0568] (2) Centrifuge for 5 minutes in a centrifuge to remove surface moisture from the material at a speed of 1000 rpm to 1500 rpm;

[0569] (3) Take out the absorbent paper and record its actual mass, weigh it together with the adhesive and record the mass M3;

[0570] (4) Calculate the water absorption rate (ω) according to the following formula: ω=(M1+M3-M2) / M2.

[0571] In the following examples, regarding the dielectric constant of the organic solvents in the electrolyte slurry, p-xylene and pseudotrimethylbenzene are used as examples. The dielectric constant of p-xylene is approximately 2.25, and the dielectric constant of pseudotrimethylbenzene is approximately 2.3.

[0572] The dielectric constant of organic solvents was determined using the frequency method: the organic solvent to be tested was injected into the capacitance meter until it was full; the frequency f of the AC power supply was set, and the power supply was connected to the capacitance meter; the capacitance value C at different frequencies was measured and recorded; according to the following formula... The dielectric constant ε of the organic solvent was calculated; the meaning of each symbol can be found in the previous text.

[0573] In the following embodiments and comparative examples, unless otherwise stated, the steps involving sulfide-based electrolyte materials are performed in an argon atmosphere.

[0574] I. Preparation of Electrolyte Slurry and Solid Electrolyte Membrane

[0575] (I) Preparation of solid electrolyte membranes

[0576] Example M1. Preparation of solid electrolyte membrane

[0577] Aluminum (Al) foil with a thickness of 12 μm was sequentially cleaned with ethanol or benzene-based solvents, dried and flattened at 60℃~70℃, and then used for later use. In this example, anhydrous ethanol was used for cleaning.

[0578] A sulfide solid electrolyte Li6PS5Cl, a binder, and the organic solvent p-xylene were dispersed in a defoamer for 15 minutes at a mass ratio of 98:2:50 to form an electrolyte slurry. The binder was a combination of nitrile rubber (as a second binder) and a cyclic olefin / chain olefin copolymer (as a first binder), added via a liquid-like method. The solvent used in the liquid-like method was p-xylene, and the mass ratio of nitrile rubber to cyclic olefin / chain olefin copolymer was 0.4:0.6. In this example, the solid content of the electrolyte slurry was 66.7 wt%.

[0579] The electrolyte slurry was transferred into a glove box and coated onto a 12 μm thick Al foil using a coater and a 75 μm thick coating using a doctor blade. It was then dried at 110 °C (600 min in this example) to obtain a solid electrolyte film formed on the Al foil. The thickness after drying was approximately 60 μm.

[0580] In this example, the nitrile rubber (nitrile rubber DN401L) has a water absorption rate of 0.5%.

[0581] In this example, the cyclic olefin / chain olefin copolymer is ethylene-norbornene (manufacturer: Zeon, Japan). K22R), with a water absorption rate of less than 0.05% (approximately 0.01%), and a weight-average molecular weight of approximately 37.5 ± 2.5 kDa, approximately 35 kDa to 40 kDa.

[0582] Example M2. A solid electrolyte membrane was prepared using essentially the same method as in Example M1, except that the mass ratio of the sulfide solid electrolyte to the cyclic olefin / chain olefin copolymer was changed to 0.1:0.9 when preparing the electrolyte slurry. The remaining operating steps were the same as in Example M1.

[0583] Example M3. A solid electrolyte membrane was prepared using essentially the same method as in Example M1, except that the mass ratio of the sulfide solid electrolyte to the cyclic olefin / chain olefin copolymer was changed to 0.5:0.5 when preparing the electrolyte slurry. The remaining operating steps were the same as in Example M1.

[0584] Example M4. A solid electrolyte membrane was prepared using essentially the same method as in Example M1, except that the mass ratio of the sulfide solid electrolyte to the cyclic olefin / chain olefin copolymer was changed to 0.6:0.4 when preparing the electrolyte slurry. The remaining operating steps were the same as in Example M1.

[0585] Example M5. A solid electrolyte membrane was prepared using essentially the same method as in Example M1, except that the mass ratio of the sulfide solid electrolyte to the cyclic olefin / chain olefin copolymer was changed to 0.7:0.3 when preparing the electrolyte slurry. The remaining operating steps were the same as in Example M1.

[0586] Example M6. A solid electrolyte membrane was prepared using essentially the same method as in Example M1, except that the mass ratio of the sulfide solid electrolyte to the cyclic olefin / chain olefin copolymer was changed to 0.85:0.15 when preparing the electrolyte slurry. The remaining operating steps were the same as in Example M1.

[0587] Example M7. A solid electrolyte membrane was prepared using essentially the same method as in Example M1, except that the mass ratio of the sulfide solid electrolyte to the cyclic olefin / chain olefin copolymer was changed to 0.25:0.75 when preparing the electrolyte slurry. The remaining operating steps were the same as in Example M1.

[0588] Comparative Example M8: A solid electrolyte membrane was prepared using a method essentially the same as that used in Example M1, except that when preparing the electrolyte slurry, the nitrile rubber in the binder was replaced with an equal mass of cyclic olefin / chain olefin copolymer.

[0589] The raw material source for the cyclic olefin / chain olefin copolymer is the same as that in Example M1.

[0590] Examples M9-11. Solid electrolyte membranes were prepared using a method essentially the same as that used in Example M1, except that the type of the first binder, a cyclic olefin / chain olefin copolymer, was changed. The first binder was a norbornene-ethylene copolymer synthesized by the aforementioned method, with a weight-average molecular weight in the range of 55kDa to 65kDa and a water absorption rate of less than 0.05%, further less than 0.03%. The water absorption rate of the norbornene-ethylene copolymer in Examples M11, M10, and M9 decreased sequentially.

[0591] In Example M9, the molar ratio of norbornene units to ethylene units in the norbornene-ethylene copolymer is 75:28, the weight-average molecular weight is approximately 58.4 kDa, and the number-average molecular weight is approximately 23.6 kDa.

[0592] In Example M10, the molar ratio of norbornene units to ethylene units in the norbornene-ethylene copolymer is 84:16, the weight-average molecular weight is approximately 61.3 kDa, and the number-average molecular weight is approximately 25.3 kDa.

[0593] In Example M11, the molar ratio of norbornene units to ethylene units in the norbornene-ethylene copolymer is 44:56, the weight-average molecular weight is approximately 63.7 kDa, and the number-average molecular weight is approximately 26.2 kDa.

[0594] In Example M12, a solid electrolyte membrane was prepared using a method essentially the same as that in Example M1, except that the type of the second binder was changed.

[0595] In this example, the second adhesive is a block copolymer (block copolymer SEBS-4055) with a water absorption rate of approximately 1.3%.

[0596] Example M13. A solid electrolyte membrane was prepared using essentially the same method as in Example M1, except that the solvent p-xylene was changed to pseudotrimethylbenzene. The remaining steps were the same as in Example M1.

[0597] Comparative Example m1: A solid electrolyte membrane was prepared using a method essentially the same as that used in Example M1, except that the cyclic olefin / chain olefin copolymer in the binder was replaced with an equal mass of nitrile rubber when preparing the electrolyte slurry.

[0598] The raw material source for nitrile rubber is the same as that in Example M1.

[0599] Comparative Example m2: A solid electrolyte membrane was prepared using essentially the same method as in Example M1, except that the cyclic olefin / chain olefin copolymer in the binder was replaced with an equal mass of PEPMNB (poly(ethylene)-co-propylene-co-5-methylene-2-norbornene) copolymer (CAS: 25038-36-2), in which the cyclic structure is located on the side groups of the chain backbone, and the water absorption rate is approximately 0.11%.

[0600] The raw material source for nitrile rubber is the same as that in Example M1.

[0601] (II) Preparation of electrolyte electrode sheets (Preparation of electrolyte negative electrode sheets)

[0602] Examples J1 to J12: Solid electrolyte membranes were formed on the film-forming substrate using essentially the same method as in Examples M1 to M12, except that the film-forming substrate was changed to the negative electrode active material layer of the negative electrode sheet to obtain the electrolyte negative electrode sheet.

[0603] The negative electrode sheet is prepared by uniformly mixing the negative electrode active material silicon-carbon composite material, the binder polyvinylidene fluoride (PVDF) and N-methylpyrrolidone in a mass ratio of 97:3:100, coating it on both sides of a copper foil, and then cold pressing it to obtain the negative electrode sheet.

[0604] The silicon-carbon composite material consists of a porous carbon matrix and nano-elemental silicon located in the pores of the porous carbon matrix, wherein the mass ratio of silicon to carbon is 1:1.

[0605] Example J13. An electrolyte negative electrode sheet was prepared using a method that was basically the same as that used in Example J1, except that the composition and preparation method of the electrolyte slurry were different.

[0606] The electrolyte slurry was prepared using essentially the same method as in Example J1, except that the solvent p-xylene was replaced with pseudotrimethylbenzene. All other operating steps remained the same, with the drying time allowed to be adjusted during the drying process.

[0607] The preparation method of the negative electrode sheet is the same as that in Example J1.

[0608] Comparative Examples j1 to j2 were prepared using essentially the same method as Comparative Examples m1 to m2, except that the electrolyte negative electrode sheets were prepared on both sides of the negative electrode active material of the negative electrode sheet by changing the coating substrate.

[0609] The preparation method of the negative electrode sheet is the same as that in Example J1.

[0610] (III) Solid-state battery fabrication

[0611] Examples 1 to 13 use electrolyte negative electrode sheets J1 to J13 to prepare all-solid-state batteries respectively, and Comparative Examples 1 and 2 use electrolyte negative electrode sheets j1 to j2 to prepare all-solid-state batteries respectively. The remaining operation steps are the same, and the drying time is allowed to be adjusted in the drying step.

[0612] The preparation method of solid-state batteries is as follows:

[0613] (1) Preparation of composite cathode materials:

[0614] LiNi, the positive electrode active material 0.83 NiCo 0.12 Mn 0.05 O2, sulfide electrolyte Li6PS5Cl and binder VGCF (vapor-grown carbon fiber) were weighed in a mass ratio of 70:27.5:2.5, ground in a mortar for 30 minutes to mix evenly, and used as a composite cathode material.

[0615] (2) Examples 1 to 13 use electrolyte electrodes J1 to J13 respectively, and Comparative Examples 1 to 3 use electrolyte negative electrodes j1 to j3 respectively.

[0616] (3) Battery assembly:

[0617] The composite positive electrode material, solid electrolyte powder, and electrolyte negative electrode sheet are placed in the assembly mold in that order to assemble a solid-state battery.

[0618] In detail: 100 mg of sulfide electrolyte Li6PS5Cl powder was weighed and added to a battery mold. The mold was pressurized at 350 MPa for 5 minutes to obtain a solid electrolyte sheet (providing the second electrolyte layer). Then, a composite positive electrode material was placed on one side of the solid electrolyte sheet, and an electrolyte negative electrode sheet was placed on the other side to assemble an all-solid-state battery. The composite positive electrode material forms the positive electrode layer, the solid electrolyte membrane in the electrolyte negative electrode sheet provides the first electrolyte layer, and the negative electrode sheet in the electrolyte negative electrode sheet provides the negative electrode layer.

[0619] Comparative Example 3. A solid-state battery was prepared using a method essentially the same as that in Example 1, except that the negative electrode sheet (excluding the first electrolyte layer) from Example J1 was used instead of the electrolyte negative electrode sheet, that is, the first electrolyte layer was omitted.

[0620] (1) Preparation of composite cathode materials:

[0621] LiNi 0.83 NiCo 0.12 Mn 0.05 O2 cathode, Li6PS5Cl sulfide electrolyte and binder VGCF (vapor-grown carbon fiber) are weighed in a mass ratio of 70:27.5:2.5, ground in a mortar for 30 minutes and mixed evenly to be used as composite cathode material.

[0622] (2) The negative electrode sheet without the first electrolyte layer in Example J1 is used.

[0623] The negative electrode active material, silicon-carbon composite material, binder, polyvinylidene fluoride (PVDF), and N-methylpyrrolidone were uniformly mixed at a mass ratio of 97:3:100 and coated onto both sides of a copper foil. After cold pressing, the negative electrode sheet was obtained. The silicon-carbon composite material consists of a porous carbon matrix and nano-elemental silicon located within the pores of the porous carbon matrix, with a silicon:carbon mass ratio of 1:1.

[0624] (3) Battery assembly:

[0625] The composite positive electrode material, solid electrolyte powder, and negative electrode sheet are placed in the assembly mold in that order to assemble a solid-state battery.

[0626] In detail: 100 mg of sulfide electrolyte Li6PS5Cl powder was weighed and added to a battery mold. The mold was pressurized at 350 MPa for 5 minutes to obtain a solid electrolyte sheet (providing the second electrolyte layer). Then, a composite positive electrode material was placed on one side of the solid electrolyte sheet, and a negative electrode sheet was placed on the other side to assemble an all-solid-state battery. The composite positive electrode material forms the positive electrode layer, the solid electrolyte sheet provides the solid electrolyte layer, and the negative electrode sheet provides the negative electrode layer.

[0627] Comparative Example 4: No first electrolyte layer, but the total thickness of the solid electrolyte layer remains basically unchanged.

[0628] Solid-state batteries were prepared using a method essentially the same as that used in Comparative Example 3. The difference was that, in the battery assembly steps, the amount of sulfide electrolyte Li6PS5Cl powder used in the second electrolyte layer was adjusted, and the resulting second electrolyte layer was treated as a solid electrolyte layer. The total thickness of the solid electrolyte layer was essentially the same as the sum of the thicknesses of the first and second electrolyte layers in Example 1.

[0629] The types and amounts of binders used in the electrolyte slurry in each embodiment can also be found in Table 1.

[0630] Table 1.

[0631] (iv) Test and Analysis Methods

[0632] 1. Peel strength test of the first electrolyte layer

[0633] Samples to be tested: solid electrolyte membrane formed by forming the first electrolyte layer on aluminum foil, electrolyte negative electrode sheet, solid-state battery.

[0634] Instrument: Instron 3365 tensile testing machine.

[0635] Taking the solid electrolyte membrane and electrolyte negative electrode sheet prepared in each example as examples, the coating surface of the first electrolyte layer formed on the film-forming substrate (aluminum foil or negative electrode active material layer) is attached to a standard test plate, the peel angle is adjusted to 180°, and a tensile testing machine is used to peel it at 180°. The peel force values ​​of 50 points are obtained in the test distance of 50mm to 120mm and the average value is calculated as the test value of "peel strength" between the first electrolyte layer and the film-forming substrate.

[0636] The greater the peel strength, the higher the film-forming strength of the first electrolyte layer, and the greater the adhesion strength of the first electrolyte layer on the film-forming substrate, and the better the interfacial stability between the first electrolyte layer and the film-forming substrate.

[0637] The test results can be found in Table 2.

[0638] When the sample to be tested is a solid-state battery, the peel strength between the negative electrode layer and the solid electrolyte layer is measured.

[0639] 2. Hydrogen sulfide release test

[0640] Test membranes: solid electrolyte membrane and electrolyte negative electrode sheet with aluminum foil as substrate.

[0641] The test membrane was evenly spread in a petri dish at a dew point of -55°C. The petri dish containing the test membrane was then placed in a 50L chamber using a sealed transfer box. The sealed transfer box containing the test membrane and petri dish was quickly opened, and the 50L chamber was then sealed. A hydrogen sulfide sensor (PGM-2500) was placed inside the chamber to record the cumulative value of hydrogen sulfide in the 50L chamber in real time. The reaction continued until the detection value of the hydrogen sulfide sensor stopped increasing, indicating that the sulfide electrolyte had completely reacted with the water molecules in the chamber. An 8cm diameter fan was placed inside the chamber. Since the density of hydrogen sulfide is greater than that of air, the airflow provided by the fan prevented hydrogen sulfide gas from settling and ensured a uniform distribution of hydrogen sulfide gas within the 50L chamber, improving the reliability of the hydrogen sulfide gas concentration test. Before the test, the 50L chamber was kept in an environment with a relative humidity of 70% RH.

[0642] 3. Ionic conductivity test

[0643] Test membranes: solid electrolyte membrane and electrolyte negative electrode sheet with aluminum foil as substrate.

[0644] The determination was performed using electrochemical impedance spectroscopy (EIS). The detailed procedure was as follows: the membrane to be tested was placed on a 10 mm diameter die, clamped at 180 MPa, and then the current collector (Al foil) was connected to the electrochemical workstation at a bias voltage of 10 mV and a frequency range of 10... 6 Electrochemical impedance spectroscopy (EIS) was performed on the membrane under test in the range of Hz to 10Hz. The intersection point of the electrochemical impedance spectrum curve from the high frequency band to the low frequency band with the Z' axis was recorded as the resistance value R. The ionic conductivity σ could be calculated using formula (1):

[0645] Where d is the thickness of the membrane under test, and A is the contact area between the electrolyte sheet and the current collector. The thickness of the membrane under test includes the thickness of the film-forming substrate (aluminum foil or negative electrode sheet).

[0646] 4. Battery performance test

[0647] The battery was tested using a constant current charge-discharge mode at room temperature (25±3℃). The solid-state battery under test was first charged and discharged at a constant current of 0.1C for 3 cycles to obtain the initial capacity C1 of the battery. Then, it was charged and discharged at 0.33C for 200 cycles, and the cycle capacity retention rate of the battery was calculated. The capacity retention rate of the nth cycle = Cn / C1×100%, where n is a positive integer.

[0648] Battery testing window is 2.0V-4.3V vs. Li + / Li (Li potential, active ion is Li) + ), where 1C = 200mA / g.

[0649] The test results can be found in Table 3, "Capacity retention rate after 200 cycles (0.33C)".

[0650] Test Results and Analysis

[0651] In Examples 1-13, a first binder with low water absorption was introduced into the electrolyte slurry. Compared to Comparative Examples 1 and 2, which did not have a first binder with low water absorption, the hydrogen sulfide release in the solid electrolyte membranes prepared in Examples M1-M12 and the electrolyte negative electrode sheets prepared in Examples J1-J13 was significantly reduced. Furthermore, they all exhibited better ionic conductivity. See Tables 2 and 3 for details. In addition, the first electrode layer (negative electrode layer) and the solid electrolyte layer in the solid-state batteries prepared in Examples 1-13 showed good adhesion strength. In the electrolyte negative electrode sheets prepared in Examples J1-J13, the first electrolyte layer exhibited high peel strength relative to the negative electrode active material layer. Correspondingly, in the solid-state batteries, the first electrolyte layer exhibited high adhesion strength relative to the negative electrode layer, providing a stable negative electrode layer / solid electrolyte layer interface. All solid-state batteries prepared in Examples 1-13 exhibited good cycle performance and high cycle capacity retention.

[0652] Furthermore, in comparative examples j3 and j4, omitting the first electrolyte layer reduced the adhesion strength between the negative electrode layer and the solid electrolyte layer, resulting in a decrease in cycle performance.

[0653] Table 2.

[0654] Table 3.

[0655] The descriptions of the various implementation methods and embodiments above tend to emphasize the differences between them. Similarities or resemblances can be referenced interchangeably, and for the sake of brevity, they will not be repeated here. The technical features of the implementation methods and embodiments described above can be combined arbitrarily. For the sake of brevity, not all possible combinations of the technical features in the above embodiments have been described. However, as long as the combinations of these technical features do not contradict each other, they should be considered within the scope of this specification.

[0656] It should be noted that this application is not limited to the above-described embodiments and examples. The above-described embodiments and examples are merely examples, and any embodiments and examples that have the same structure and achieve the same effect as the technical concept within the scope of this application are included in the technical scope of this application. The embodiments and examples described above only illustrate several embodiments and examples of this application, and although the descriptions are relatively detailed, they should not be construed as limiting the scope of the patent. Furthermore, various modifications that can be conceived by those skilled in the art to the embodiments or examples, and other ways of constructing embodiments or examples by combining some of the constituent elements of the embodiments or examples, are also included in the scope of this application without departing from the spirit of this application.

Claims

1. A solid electrolyte membrane, comprising a first electrolyte layer, the first electrolyte layer comprising a first solid electrolyte and a first binder layer; in, The first solid electrolyte includes a sulfide solid electrolyte; the first layer binder includes a first binder, the water absorption rate of the first binder being less than or equal to 0.1%.

2. The solid electrolyte membrane according to claim 1, wherein, The first binder comprises a cyclic olefin / chain olefin copolymer, wherein the monomer units of the cyclic olefin / chain olefin copolymer include cyclic olefin monomer units and chain olefin monomer units, and the chain backbone of the cyclic olefin / chain olefin copolymer includes a cyclic structure provided by the cyclic olefin monomer units.

3. A solid electrolyte membrane comprising a first electrolyte layer, the first electrolyte layer comprising a sulfide solid electrolyte and a first adhesive layer, the first adhesive layer comprising a first binder; in, The first binder comprises a cyclic olefin / chain olefin copolymer, wherein the monomer units of the cyclic olefin / chain olefin copolymer include cyclic olefin monomer units and chain olefin monomer units, and the chain backbone of the cyclic olefin / chain olefin copolymer includes a cyclic structure provided by the cyclic olefin monomer units.

4. The solid electrolyte membrane according to claim 3, wherein, The first adhesive satisfies one or more of the following characteristics: The chain backbone of the cyclic olefin / chain olefin copolymer is a carbon backbone; The cyclic olefin / chain olefin copolymer is an aliphatic polymer; The cyclic structure in the cyclic olefin monomer unit includes one or more of monocyclic and polycyclic structures; The number of ring atoms in the cyclic olefin monomer unit is 3 to 30; The olefin monomer unit includes those corresponding to C. 2～6 The structural unit of olefins; The side groups of the cyclic olefin / chain olefin copolymer include C 1～20 Aliphatic chains and fluorinated C 1～20 One or more of the aliphatic chains; In the cyclic olefin / chain olefin copolymer, the molar fraction of the cyclic olefin monomer unit is 10% to 85%; In the cyclic olefin / chain olefin copolymer, the molar fraction of the chain olefin monomer unit is 15% to 90%; The weight-average molecular weight of the cyclic olefin / chain olefin copolymer is 30 kDa to 100 kDa.

5. The solid electrolyte membrane according to claim 4, wherein, The first adhesive satisfies one or more of the following characteristics: The number of ring atoms in the cyclic olefin monomer unit is 5 to 20; The cyclic olefin monomer unit includes structural units corresponding to one or more monomers selected from norbornene, cyclopentene, cyclohexene, and cycloheptene; The olefin monomer unit includes structural units corresponding to one or more monomers of ethylene and propylene; optionally, the olefin monomer unit includes structural units corresponding to ethylene. The side groups of the cyclic olefin / chain olefin copolymer include C 1～20 Alkyl chains and fluorinated C 1～20 One or more of the alkyl chain; In the cyclic olefin / chain olefin copolymer, the molar fraction of the cyclic olefin monomer unit is 30% to 85%; In the cyclic olefin / chain olefin copolymer, the molar fraction of the chain olefin monomer unit is 15% to 70%. The weight-average molecular weight of the cyclic olefin / chain olefin copolymer is 30 kDa to 50 kDa.

6. The solid electrolyte membrane according to any one of claims 3 to 5, wherein, The cyclic olefin / chain olefin copolymers include one or more of the following: (ethylene-cyclopentene) copolymers, (ethylene-norbornene) random copolymers, and (ethylene-norbornene) alternating copolymers.

7. The solid electrolyte membrane according to any one of claims 1 to 6, wherein, The water absorption rate of the first adhesive is less than or equal to 0.05%; optionally, the water absorption rate of the first adhesive is less than or equal to 0.02%; further optionally, the water absorption rate of the first adhesive is less than or equal to 0.01%.

8. The solid electrolyte membrane according to any one of claims 1 to 7, wherein, The first electrolyte layer satisfies one or more of the following characteristics: The weight percentage of the first adhesive in the first layer of adhesive is 15% to 100%, and optionally 40% to 95%; The first adhesive has a weight percentage of 0.3% to 6% in the first electrolyte layer, and can be optionally 0.3% to 4%. The sulfide solid electrolyte constitutes 94% to 99.5% of the weight of the first electrolyte layer.

9. The solid electrolyte membrane according to claim 8, wherein, The first electrolyte layer satisfies one or more of the following characteristics: The weight percentage of the first adhesive in the first layer of adhesive is 50% to 75%; The first adhesive comprises 0.5% to 2% by weight in the first electrolyte layer; The sulfide solid electrolyte accounts for 95% to 98% of the weight of the first electrolyte layer.

10. The solid electrolyte membrane according to any one of claims 1 to 9, wherein, The first adhesive layer further includes a second adhesive, the second adhesive having a water absorption rate greater than or equal to 0.5%, optionally greater than or equal to 1%, and further optionally greater than or equal to 2%.

11. The solid electrolyte membrane according to claim 10, wherein, The second adhesive includes one or more of nitrile rubber, styrene-butadiene rubber, hydrogenated nitrile rubber, natural rubber, etherified cellulose, polymethyl methacrylate, polyethylene oxide methyl vinyl silicone rubber, and derivatives of any of the foregoing; wherein the water absorption rate of the derivative is ≥0.5%; Optionally, the second adhesive includes at least one of nitrile rubber and nitrile rubber derivatives, wherein the nitrile rubber derivatives include hydrogenated nitrile rubber.

12. The solid electrolyte membrane according to claim 10 or 11, wherein, The first electrolyte layer satisfies one or more of the following characteristics: The second adhesive accounts for 0% to 85% of the weight of the first adhesive layer, and is optionally 5% to 60%. The sum of the weight percentages of the first adhesive and the second adhesive in the first electrolyte layer is 0.5% to 6%; The weight percentage of the first adhesive in the sum of the weights of the first adhesive and the second adhesive is 15% to 100%, and optionally 40% to 95%. The weight percentage of the second adhesive in the sum of the weights of the first adhesive and the second adhesive is 0% to 85%, and optionally 5% to 60%.

13. The solid electrolyte membrane according to claim 12, wherein, The first electrolyte layer satisfies one or more of the following characteristics: The weight percentage of the first adhesive in the first layer of adhesive is 50% to 75%; The second adhesive accounts for 25% to 50% of the weight of the first adhesive layer; The first adhesive accounts for 0.5% to 2% of the weight of the first electrolyte layer; The sum of the weight percentages of the first adhesive and the second adhesive in the first electrolyte layer is 2% to 5%; The sulfide solid electrolyte has a weight percentage of 95% to 98% in the first electrolyte layer; The weight of the first adhesive accounts for 50% to 75% of the total weight of the first adhesive and the second adhesive; The weight of the second adhesive accounts for 25% to 50% of the total weight of the first adhesive and the second adhesive.

14. The solid electrolyte membrane according to any one of claims 1 to 8, wherein, The first layer of adhesive includes cyclic olefin / chain olefin copolymers, and also includes one or more of nitrile rubber, styrene-butadiene rubber, hydrogenated nitrile rubber, natural rubber, polyvinylidene fluoride, etherified cellulose, polymethyl methacrylate, and polyoxyethylene methyl vinyl silicone rubber.

15. The solid electrolyte membrane according to any one of claims 1 to 14, wherein, The sulfide solid electrolyte includes one or more of the following: LGPS type sulfide electrolyte, silver-germanium sulfide type sulfide electrolyte, lithium sulfide-phosphorus pentasulfide complex sulfide electrolyte, and thio-LISICON sulfide electrolyte.

16. The solid electrolyte membrane according to claim 15, wherein, The sulfide solid electrolyte includes Li 6-x PS 5-x Cl 1+x , where 0≤x≤0.

9.

17. The solid electrolyte membrane according to any one of claims 1 to 16, wherein, The thickness of the first electrolyte layer is 15μm to 75μm, and can be selected as 25μm to 50μm.

18. An electrolyte electrode, wherein, The electrolyte electrode includes an electrode body and a solid electrolyte membrane located on at least one side of the electrode body; the solid electrolyte membrane is the solid electrolyte membrane according to any one of claims 1 to 17; Alternatively, the electrolyte electrode may include an electrode body and a first electrolyte layer located on at least one side of the electrode body, wherein the first electrolyte layer is the first electrolyte layer as defined in any one of claims 1 to 17.

19. The electrolyte electrode according to claim 18, wherein, The electrolyte electrode sheet is an electrolyte negative electrode sheet, and the electrode body is a negative electrode body; Optionally, the negative electrode body includes a negative electrode current collector and a negative electrode active material layer located on at least one side of the negative electrode current collector, wherein the first electrolyte layer is located on the side of the negative electrode active material layer away from the negative electrode current collector.

20. A solid-state battery, wherein, It includes at least one of the first electrolyte layer as defined in any one of claims 1 to 17, the solid electrolyte membrane as described in any one of claims 1 to 17, and the electrolyte electrode as described in claim 18 or 19.

21. A solid-state battery, wherein, The solid-state battery includes a first electrode layer, a solid electrolyte layer, and a second electrode layer stacked sequentially; wherein, the solid electrolyte layer includes a first electrolyte layer, and the first electrolyte layer is located on the side of the solid electrolyte layer closer to the first electrode layer; Wherein, the first electrolyte layer comprises a first solid electrolyte and a first binder layer, the first solid electrolyte comprising a sulfide solid electrolyte, and the first binder layer comprising a first binder; the first binder satisfies one or both of the following characteristics: (t1) The water absorption rate of the first adhesive is less than or equal to 0.1%; (t2) The first binder comprises a cyclic olefin / chain olefin copolymer, wherein the monomer units of the cyclic olefin / chain olefin copolymer include cyclic olefin monomer units and chain olefin monomer units, and the chain backbone of the cyclic olefin / chain olefin copolymer includes a cyclic structure provided by the cyclic olefin monomer units.

22. The solid-state battery according to claim 21, wherein, The first electrolyte layer is as defined in any one of claims 2, 4 to 17.

23. The solid-state battery according to claim 21 or 22, wherein, The solid electrolyte layer further includes a second electrolyte layer, which is located between the second electrode layer and the first electrolyte layer; The second electrolyte layer includes a second solid electrolyte and optionally includes a second binder.

24. The solid-state battery according to claim 23, wherein, It meets one or more of the following characteristics: The total thickness of the solid electrolyte layer is greater than or equal to 55 μm, and can be selected as 60 μm to 110 μm; The thickness of the second electrolyte layer is greater than or equal to 30 μm, and can be selected as 35 μm to 60 μm; The thickness of the second electrolyte layer is greater than the thickness of the first electrolyte layer; The content of the second binder in the second electrolyte layer is lower than the content of the first binder in the first electrolyte layer, by weight percentage; The second adhesive layer has a weight percentage of 0 wt% to 2 wt% in the second electrolyte layer; The second solid electrolyte accounts for 98 wt% to 100 wt% of the weight of the second electrolyte layer.

25. The solid-state battery according to any one of claims 21 to 24, wherein, The solid-state battery satisfies one or more of the following characteristics: The first electrode layer is a negative electrode layer, and the second electrode layer is a positive electrode layer; optionally, the negative electrode layer includes a negative electrode current collector and a negative electrode active material layer located on at least one side of the negative electrode current collector, and the first electrolyte layer is located on the side of the negative electrode active material layer away from the negative electrode current collector; The solid-state battery is an all-solid-state battery.

26. A method for preparing a solid electrolyte membrane, comprising the following steps: Prepare an electrolyte slurry comprising a first solid electrolyte, a first binder, and an organic solvent; wherein, The first solid electrolyte includes a sulfide solid electrolyte, and the first layer binder includes a first binder; The electrolyte slurry is coated onto a film-forming substrate and dried to form a solid electrolyte film on the film-forming substrate. Wherein, the first adhesive satisfies one or two of the following characteristics: (t1) The water absorption rate of the first adhesive is less than or equal to 0.1%; (t2) The first binder includes a cyclic olefin / chain olefin copolymer, wherein the monomer units of the cyclic olefin / chain olefin copolymer include cyclic olefin monomer units and chain olefin monomer units, and the chain backbone of the cyclic olefin / chain olefin copolymer includes a cyclic structure provided by the cyclic olefin monomer units; Optionally, the solid electrolyte membrane is prepared by the method described in any one of claims 2, 4 to 17.

27. A method for preparing a solid-state battery, comprising the following steps: Preparation of electrolyte electrodes; wherein, The electrolyte electrode includes a first electrode layer and a first electrolyte layer located on at least one side of the first electrode layer; wherein, the first electrolyte layer includes a first solid electrolyte and a first binder layer, the first solid electrolyte including a sulfide solid electrolyte, and the first binder layer including a first binder; A second electrode layer is formed on the side of the first electrolyte layer away from the first electrode layer; Wherein, the first adhesive satisfies one or two of the following characteristics: (t1) The water absorption rate of the first adhesive is less than or equal to 0.1%; (t2) The first binder includes a cyclic olefin / chain olefin copolymer, wherein the monomer units of the cyclic olefin / chain olefin copolymer include cyclic olefin monomer units and chain olefin monomer units, and the chain backbone of the cyclic olefin / chain olefin copolymer includes a cyclic structure provided by the cyclic olefin monomer units; Optionally, the electrolyte electrode is as defined in claim 18 or 19, or the first electrolyte layer is as defined in any one of claims 2, 4 to 17.

28. The method for preparing a solid-state battery according to claim 27, wherein, The first electrolyte layer is formed on at least one side of the first electrode layer by coating and drying an electrolyte slurry; The electrolyte slurry comprises the first solid electrolyte, the first layer binder, and an organic solvent.

29. The method for preparing a solid-state battery according to claim 28, wherein, The electrolyte electrode is an electrolyte negative electrode, and the method for preparing the solid-state battery includes the following steps: The electrolyte slurry is coated onto at least one surface of the negative electrode sheet and dried to prepare the electrolyte negative electrode sheet; wherein the negative electrode sheet forms a negative electrode layer, and the dried electrolyte slurry forms the first electrolyte layer; A second electrolyte layer and a positive electrode layer are formed sequentially on the side of the first electrolyte layer away from the negative electrode layer.

30. The method for preparing a solid-state battery according to claim 28 or 29, wherein, The dielectric constant ε of the organic solvent in the electrolyte slurry satisfies: ε≤6.

5.

31. The method for preparing a solid-state battery according to claim 30, wherein, The organic solvent satisfies one or more of the following characteristics: The organic solvent includes one or more of low-polarity solvents and non-polar solvents; wherein, the dielectric constant ε1 of the low-polarity solvent satisfies: 2.6 < ε1 ≤ 6.5; and the dielectric constant ε2 of the non-polar solvent satisfies: ε2 ≤ 2.

6. The organic solvent includes substituted benzene, wherein the phenyl group in the substituted benzene is replaced by one or more substituents selected from the substituent group G, the substituent group G including: methyl, chlorine atom and methoxy; The organic solvent has a weight percentage of 50 wt% to 100 wt%, and is optionally 70 wt% to 100 wt%. The organic solvent includes one or more of xylene, butyl butyrate, octyl butyrate, trimethylbenzene, toluene, chlorobenzene, dimethyl carbonate, ethyl acetate, n-hexane, anisole, dibromomethane, triethyl phosphate, isopropyl ether, and benzyl acetate; optionally, the organic solvent includes one or more of p-xylene, pseudotrimethylbenzene, toluene, butyl butyrate, and octyl butyrate. The organic solvent in the electrolyte slurry is 30 wt% to 90 wt%, and optionally 40 wt% to 70 wt%.

32. The method for preparing a solid-state battery according to any one of claims 27 to 31, wherein it satisfies one or more of the following characteristics: The electrolyte electrode sheet is the electrolyte electrode sheet according to claim 18 or 19, and the first electrode layer includes a corresponding electrode body; The solid-state battery prepared is the solid-state battery according to any one of claims 20 to 25.

33. An electrical device comprising at least one of the following: a solid electrolyte membrane according to any one of claims 1 to 17; an electrolyte electrode according to claim 18 or 19; a solid-state battery according to any one of claims 20 to 25; a solid electrolyte membrane prepared by the method of preparing the solid electrolyte membrane according to claim 26; and a solid-state battery prepared by the method of preparing any one of claims 27 to 32.

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