TWI848579B - Solid electrolyte and electrode surface processing method for solid state battery - Google Patents
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 7
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
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Abstract
Description
本發明是有關一種應用於固態電池之固體電解質和電極介面處理方法，特別是一種提高固態電池之壽命與增加可靠度之製備方法。The present invention relates to a method for treating the interface between a solid electrolyte and an electrode used in a solid-state battery, and in particular to a method for improving the life and reliability of the solid-state battery.
固態電池是使用固體電極和固體電解質層的一種電池，也是鋰電池家族成員之一，相較傳統鋰電池電解液是液態，而固態電池使用的電解液則是固態，並解決液態電池安全問題和能量密度之缺點。Solid-state batteries are a type of battery that uses solid electrodes and solid electrolyte layers. They are also a member of the lithium battery family. Compared to traditional lithium batteries, which use liquid electrolytes, solid-state batteries use solid electrolytes, and solve the safety issues and energy density shortcomings of liquid batteries.
固態電池具有高安全性的特性，由於固態電池改用固態電解質，沒有漏液汙染、易燃爆炸等問題，且電解質為固態，電池不會因為隔離層破損就導致正負極接觸短路爆炸，故安全性較高。Solid-state batteries have the characteristics of high safety. Since solid-state batteries use solid electrolytes, there are no problems such as leakage pollution, flammability and explosion. Moreover, the electrolyte is solid, and the battery will not cause a short circuit and explosion due to the damage of the isolation layer, so it is safer.
固態電池具有高能量密度的特性，由於固態電池的安全性，故正負極可以選用能量密度更高的材料，如負極採用鋰金屬或是正極採用NCMA混合物等，使其能量密度有機會超過鋰三元電池。固態電解質能量密度與相同體積的液態鋰離子電池相比，可以有更高電池存儲能量，充放電速度也快。Solid-state batteries have the characteristics of high energy density. Due to the safety of solid-state batteries, materials with higher energy density can be selected for the positive and negative electrodes, such as lithium metal for the negative electrode or NCMA mixture for the positive electrode, so that its energy density has the opportunity to exceed that of lithium ternary batteries. Compared with liquid lithium-ion batteries of the same volume, the energy density of solid electrolytes can have higher battery storage energy and faster charging and discharging speeds.
固態電池具有體積小的特性，由於固態電池更輕巧，封裝更簡易，體積能量密度大幅提升，且也不需要鋰離子電池的監測、冷卻和保溫系統，汽車底盤能空出更多空間放置電池，也助於增加電動車續航力。Solid-state batteries have the characteristics of small size. Since solid-state batteries are lighter and easier to package, their volume energy density is greatly improved. They also do not require the monitoring, cooling and insulation systems of lithium-ion batteries. More space can be left in the car chassis to place batteries, which also helps to increase the endurance of electric vehicles.
綜上所述，固態電池有非常多的優點，然而目前對於固態鋰電池，仍有問題亟需解決，一般傳統液態電解質的室溫離子電導率約為10 -2S/cm，與之相比，無論是聚合物、氧化物還是硫化物材料體系，均存在數量級上的差距。 In summary, solid-state batteries have many advantages. However, there are still problems that need to be solved for solid-state lithium batteries. The room-temperature ionic conductivity of traditional liquid electrolytes is about 10 -2 S/cm. In comparison, there is an order of magnitude difference in the material systems of polymers, oxides, and sulfides.
聚合物材料體系來講，一般分為乾態和凝膠聚合物電解質兩種，其中乾態聚合物電解質室溫離子電導率較低，故實際應用的可能性低；而凝膠聚合物電解質大部分由高分子絡合鋰鹽、浸潤溶劑構成的，故仍是存在活性物質的溶解穿梭以及金屬鋰枝晶的生成問題。In terms of polymer material systems, they are generally divided into dry and gel polymer electrolytes. Dry polymer electrolytes have a relatively low room temperature ionic conductivity, so the possibility of practical application is low; while gel polymer electrolytes are mostly composed of polymer complexes, lithium salts, and wetting solvents, so there are still problems with the dissolution and shuttling of active substances and the formation of metal lithium dendrites.
以氧化物還是硫化物材料體系來講，在電極與電解質介面上，傳統液態電解質與正、負極的接觸方式為液/固接觸，介面潤濕性良好，介面之間不會產生大的阻抗，相比較之下，固態電解質與正負極之間以固/固介面的方式接觸，接觸面積小，與極片的接觸緊密性較差，介面阻抗較高，鋰離子在介面之間的傳輸受阻。而低離子電導率和高介面阻抗導致的高內阻，使得鋰離子在固態電池內部傳輸效率低，直接影響電池的能量密度與功率密度，在高倍率大電流下的傳輸能力差，因此會影響電池的快充性能與增加長期使用的風險及減少電池使用的壽命。In terms of oxide or sulfide material systems, at the interface between the electrode and the electrolyte, the traditional liquid electrolyte contacts the positive and negative electrodes in a liquid/solid manner, the interface has good wettability, and no large impedance is generated between the interfaces. In contrast, the solid electrolyte contacts the positive and negative electrodes in a solid/solid manner, with a small contact area, poor contact tightness with the electrodes, high interface impedance, and hindered transmission of lithium ions between the interfaces. The high internal resistance caused by low ionic conductivity and high interface impedance makes the lithium ion transmission efficiency inside the solid-state battery low, which directly affects the energy density and power density of the battery. The transmission capacity is poor under high rate and high current, which will affect the fast charging performance of the battery, increase the risk of long-term use, and reduce the life of the battery.
綜上所述，固態電池仍有很大問題需要解決，其中介面阻抗與及金屬鋰枝晶的問題，都會與固體電解質層或是電極層（正極層、負極層）之表面缺陷有關，尤其是表面缺陷處容易形成大型局部性的鋰凸（Dendride），一般有以下幾種表面缺陷，有顆粒污染（Particle contamination）、表面粗糙度（Surface roughness）、表面裂紋（Surface cracks）、表面污染（Surface contamination）、點缺陷（Point defects）、位錯（Dislocations）、微裂紋（Microcracks）、雜質（Impurities），其中以點缺陷（Point defects）、位錯（Dislocations）、微裂紋（Microcracks）、雜質（Impurities）、表面污染（Surface contamination）會造成影響最大，若是沒有處理好，則容易導致大型局部性的鋰凸的問題發生。In summary, solid-state batteries still have many problems to be solved, among which the interface impedance and metal lithium dendrite problems are related to the surface defects of the solid electrolyte layer or the electrode layer (positive electrode layer, negative electrode layer). In particular, large local lithium protrusions (Dendride) are easily formed at the surface defects. Generally, there are the following types of surface defects: particle contamination, surface roughness, surface cracks, surface contamination, point defects, dislocations, microcracks, and impurities. Point defects, dislocations, microcracks, impurities, and surface contamination are the most common. Contamination) will have the greatest impact. If it is not handled properly, it will easily lead to large local lithium bulge problems.
因此，若先透過原子層蝕刻處理（Atomic Layer Etching, ALE），對固體電解質層朝向該正極層及該負極層之表面，進行原子層蝕刻處理，以進行表面處理，之後，再以原子層沉積處理（Atomic Layer Deposition, ALD）將保護層沉積形成於該固體電解質層與該正極層之間及該固體電解質層與該負極層之間，用以減少大型局部性的鋰凸（Dendride）形成，進而降低正副極短路之問題，如此將能夠提高電池可靠度與使用壽命，因此本發明應為一最佳解決方案。Therefore, if the surface of the solid electrolyte layer facing the positive electrode layer and the negative electrode layer is first etched by atomic layer etching (ALE) for surface treatment, and then a protective layer is deposited between the solid electrolyte layer and the positive electrode layer and between the solid electrolyte layer and the negative electrode layer by atomic layer deposition (ALD) to reduce the formation of large local lithium convexities (dendride), thereby reducing the problem of short circuit between the positive and negative electrodes, the reliability and service life of the battery can be improved. Therefore, the present invention should be an optimal solution.
本發明應用於固態電池之固體電解質和電極介面處理方法，其中該固態電池係包含有一正極層、一負極層及一形成於該正極層及該負極層之間的固體電解質層，而該表面處理方法為： (1) 於該固體電解質層朝向該正極層之表面，進行原子層蝕刻處理，用以進行表面處理； (2) 進行原子層沉積處理，於該固體電解質層與該正極層之間形成有一第一保護層及一第二保護層，該第一保護層之成份係為氧化鋁，而該第二保護層之成份係為氮氧化矽或氮化矽。 The present invention is applied to a solid electrolyte and electrode interface treatment method of a solid battery, wherein the solid battery comprises a positive electrode layer, a negative electrode layer and a solid electrolyte layer formed between the positive electrode layer and the negative electrode layer, and the surface treatment method is: (1) performing an atomic layer etching treatment on the surface of the solid electrolyte layer facing the positive electrode layer for surface treatment; (2) performing an atomic layer deposition treatment to form a first protective layer and a second protective layer between the solid electrolyte layer and the positive electrode layer, wherein the first protective layer is composed of aluminum oxide, and the second protective layer is composed of silicon oxynitride or silicon nitride.
更具體的說，所述原子層蝕刻處理用以移除該固體電解質層表面上的缺陷。More specifically, the atomic layer etching process is used to remove defects on the surface of the solid electrolyte layer.
更具體的說，所述第一保護層與該第二保護層之總和厚度係小於10nm。More specifically, the total thickness of the first protective layer and the second protective layer is less than 10 nm.
更具體的說，所述正極層朝向該固體電解質層之表面更能夠進行原子層蝕刻處理，用以進行表面處理，以移除該正極層表面上的缺陷。More specifically, the surface of the positive electrode layer facing the solid electrolyte layer can be further subjected to atomic layer etching for surface treatment to remove defects on the surface of the positive electrode layer.
更具體的說，所述第一保護層係鄰近於該固體電解質層，而該第二保護層係鄰近於該正極層。More specifically, the first protective layer is adjacent to the solid electrolyte layer, and the second protective layer is adjacent to the positive electrode layer.
本發明應用於固態電池之固體電解質和電極介面處理方法，其中該固態電池係包含有一正極層、一負極層及一形成於該正極層及該負極層之間的固體電解質層，而該表面處理方法為： (1) 於該固體電解質層朝向該正極層及該負極層之表面，進行原子層蝕刻處理，用以進行表面處理； (2) 進行原子層沉積處理，於該固體電解質層與該正極層之間及該固體電解質層與該負極層之間，皆形成有一第一保護層及一第二保護層，該第一保護層之成份係為氧化鋁，而該第二保護層之成份係為氮氧化矽或氮化矽。 The present invention is applied to a solid electrolyte and electrode interface treatment method of a solid battery, wherein the solid battery comprises a positive electrode layer, a negative electrode layer and a solid electrolyte layer formed between the positive electrode layer and the negative electrode layer, and the surface treatment method comprises: (1) performing atomic layer etching treatment on the surface of the solid electrolyte layer facing the positive electrode layer and the negative electrode layer for surface treatment; (2) Atomic layer deposition is performed to form a first protective layer and a second protective layer between the solid electrolyte layer and the positive electrode layer and between the solid electrolyte layer and the negative electrode layer. The first protective layer is composed of aluminum oxide, and the second protective layer is composed of silicon oxynitride or silicon nitride.
更具體的說，所述原子層蝕刻處理用以移除該固體電解質層表面上的缺陷。More specifically, the atomic layer etching process is used to remove defects on the surface of the solid electrolyte layer.
更具體的說，所述第一保護層與該第二保護層之總和厚度係小於10nm。More specifically, the total thickness of the first protective layer and the second protective layer is less than 10 nm.
更具體的說，所述正極層朝向該固體電解質層之表面更能夠進行原子層蝕刻處理，用以進行表面處理，以移除該正極層表面上的缺陷。More specifically, the surface of the positive electrode layer facing the solid electrolyte layer can be further subjected to atomic layer etching for surface treatment to remove defects on the surface of the positive electrode layer.
更具體的說，所述負極層朝向該固體電解質層之表面更能夠進行原子層蝕刻處理，用以進行表面處理，以移除該負極層表面上的缺陷。More specifically, the surface of the negative electrode layer facing the solid electrolyte layer can be further subjected to atomic layer etching for surface treatment to remove defects on the surface of the negative electrode layer.
更具體的說，所述第一保護層係鄰近於固體電解質層，而該第二保護層係鄰近於該正極層及該負極層。More specifically, the first protective layer is adjacent to the solid electrolyte layer, and the second protective layer is adjacent to the positive electrode layer and the negative electrode layer.
有關於本發明其他技術內容、特點與功效，在以下配合參考圖式之較佳實施例的詳細說明中，將可清楚的呈現。Other technical contents, features and effects of the present invention will be clearly presented in the following detailed description of the preferred embodiments with reference to the drawings.
請參閱第1圖所示，應用於固態電池之第一實施表面處理方法如下：
(1) 於該固體電解質層朝向該正極層之表面，進行原子層蝕刻處理，用以進行表面處理101；
(2) 進行原子層沉積處理，於該固體電解質層與該正極層之間，形成有一第一保護層及一第二保護層，該第一保護層之成份係為氧化鋁，而該第二保護層之成份係為氮氧化矽或氮化矽102。
Referring to FIG. 1, the first surface treatment method for solid-state batteries is as follows:
(1) Atomic layer etching is performed on the surface of the solid electrolyte layer facing the positive electrode layer to perform
請參閱第2圖所示，固態電池1係包含有一正極層11、一負極層12及一位於該正極層11及該負極層12之間的固體電解質層13。As shown in FIG. 2 , the solid-
正極層11是陰極(cathode)，負極層12是陽極(anode)。The
正極層11由複合材料(composite material)形成，該複合材料包括可用於普通鋰電池的活性材料(active material) 、導體(conductor) 、粘合劑(binder)和無機固體電解質層(inorganic solid electrolyte)的顆粒。The
陽極活性材料(anode active material)例如可以是金屬鋰(metallic lithium) 、鋰合金,(lithium alloy) 、硬碳(hard carbon)，軟碳(soft carbon)、富勒烯(fullerene)、二氧化矽(SiO 2)、矽碳複合材料(Si/C)、二氧化鈦(TiO 2)、 二氧化錫(SnO 2)。而導體則可使用石墨烯(graphene)、碳納米管(carbon nanotubes)、科琴黑(Ketjenblack) 、活性碳(activated carbon)或氣相生長碳纖維（VGCF），當然也可以是混合其中的兩種或更多種以混合導體形式使用。至於粘合劑可包括選自聚四氟乙烯（PTFE）、聚偏二氟乙烯（PVDF）、羧甲基纖維素（CMC）、苯乙烯 - 丁二烯橡膠（SBR）和聚酰亞胺(polyimide)中的一種或多種混用。 Anode active materials can be, for example, metallic lithium, lithium alloy, hard carbon, soft carbon, fullerene, silicon dioxide (SiO 2 ), silicon carbon composite (Si/C), titanium dioxide (TiO 2 ), tin dioxide (SnO 2 ). Conductors can be graphene, carbon nanotubes, Ketjenblack, activated carbon or vapor grown carbon fiber (VGCF), and of course, two or more of them can be mixed to form a mixed conductor. The binder may include one or more selected from polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), carboxymethyl cellulose (CMC), styrene-butadiene rubber (SBR) and polyimide.
負極層12由複合材料(composite material)形成，該複合材料包括用於普通鋰電池的活性材料、導體、粘合劑和無機固體電解質層的顆粒。陰極活性材料(cathode active material)例如可以是鋰鈷複合氧化物(lithium cobalt composite oxide)、鋰鎳複合氧化物(lithium nickel composite oxide)、鋰錳複合氧化物(lithium manganese composite oxide)、鋰釩複合氧化物(lithium vanadium composite oxide)或鋰鐵複合氧化物(lithium iron composite oxide)。同樣地，石墨烯(graphene)、碳納米管(carbon nanotubes)、科琴黑(Ketjenblack) 、活性碳(activated carbon)或氣相生長碳纖維（VGCF）可以用作導體，當然也可以是混合其中的兩種或更多種以混合導體形式使用。至於粘合劑可包括選自聚四氟乙烯（PTFE）、聚偏二氟乙烯（PVDF）、羧甲基纖維素（CMC）、苯乙烯 - 丁二烯橡膠（SBR）和聚酰亞胺(polyimide)中的一種或多種混用，當然，它們中的兩種或更多種可以以混合導體的形式使用。粘合劑可以包括選自由聚四氟乙烯（PTFE）、聚偏二氟乙烯（PVDF）、羧甲基纖維素（CMC）、丁苯橡膠（SBR）和聚酰亞胺組成的組中的材料，或它們的混合物。要注意的是，以上化合物僅為示例性列出，在其他示例中，第一電極11可以是陽極，第二電極可以是陰極，並且可以使用適合於電池操作的類似或不同的化合物。The
該固體電解質層13係佈置在該正極層11、該負極層12周圍，而該正極層11、該負極層12及固體電解質層13被容納在電池的殼體中，並且第一電極11和第二電極12可以包括延伸到殼體外部的部分。The
該固體電解質層13表面或/及正極層11表面上的缺陷，能夠先透過原子層蝕刻處理（Atomic Layer Etching, ALE）來移除細微表面缺陷（點缺陷Point defects、表面污垢Surface contamination、微刮痕microscratch、細粗糙(micro sharp-edgaed surface roughness)等）。Defects on the surface of the
該固體電解質層13與該正極層11之間，於該固體電解質層13朝向該正極層11之表面透過原子層蝕刻處理來移除表面缺陷。Between the
該固體電解質層13與該正極層11之間，於該正極層11朝向該固體電解質層13之表面透過原子層蝕刻處理來移除表面缺陷。Between the
該固體電解質層13與該正極層11之間，於該固體電解質層13朝向該正極層1之表面及該正極層11朝向該固體電解質層13之表面，透過原子層蝕刻處理來移除表面缺陷。Surface defects between the
該原子層蝕刻處理（Atomic Layer Etching, ALE）之流程係為一習用技術，主要將一蝕刻氣體與一惰性氣體一起經由一質量流量控制器供應至一反應空間，再使用電漿進行蝕刻，其中向該反應空間供應惰性氣體或氮氣作為基本反應氣體以產生電漿，除此之外更能夠添加氧化氣體或是氫氣一類的還原氣體來控制蝕刻速率，其製程溫度大多控制在0度至250度。The Atomic Layer Etching (ALE) process is a common technology, which mainly supplies an etching gas and an inert gas to a reaction space through a mass flow controller, and then uses plasma for etching. Inert gas or nitrogen is supplied to the reaction space as a basic reaction gas to generate plasma. In addition, oxidizing gas or reducing gas such as hydrogen can be added to control the etching rate. The process temperature is mostly controlled at 0 to 250 degrees.
除了原子層蝕刻處理之外，更透過原子層沉積處理（Atomic Layer Deposition, ALD），將第一保護層111（成份係為氮氧化矽Al
2O
3）及第二保護層112（成份係為氮氧化矽SiO
xN
y或是Si
3N
4）沉積形成於該固體電解質層13與該正極層11之間，其中該第一保護層111係鄰近於固體電解質層13，而該第二保護層112係鄰近於正極層11。
In addition to the atomic layer etching process, the first protective layer 111 (composed of silicon oxynitride Al 2 O 3 ) and the second protective layer 112 (composed of silicon oxynitride SiO x N y or Si 3 N 4 ) are deposited between the
該原子層沉積處理（Atomic Layer Deposition, ALD）用以遮蓋較大表面缺陷（位錯Dislocations、微孔洞Microhole、微裂紋Microcracks等等）。The atomic layer deposition (ALD) process is used to cover larger surface defects (dislocations, microholes, microcracks, etc.).
上述原子層沉積處理，能夠先將第一保護層111沉積於該固體電解質層13朝向該正極層11之表面上，之後再將第二保護層112沉積於該第一保護層111上，該第二保護層112係介於該第一保護層111與該正極層11之間。The above atomic layer deposition process can first deposit the first
上述原子層沉積處理，亦能夠先將第二保護層112沉積於該正極層11朝向該固體電解質層13之表面上，之後再將該第一保護層111沉積於該第二保護層112上，該第一保護層111係介於該固體電解質層13與該第二保護層112之間。The above atomic layer deposition process can also first deposit the second
該第一保護層111與該第二保護層112之總和厚度係小於10nm。The total thickness of the first
該原子層沉積處理（Atomic Layer Deposition, ALD）之流程係為一習用技術，主要將含有欲沉積成分的化學氣體與陶瓷基板反應，再利用大量惰性氣體(例如氮氣、氬氣)將化學氣體移除，然後重複上述步驟。藉此讓所有反應只會發生在陶瓷基板表面，每一次循環的過程僅形成厚度為一層原子的薄膜，也因此讓每次鍍膜厚度的精確性達原子級(約0.1 nm)的尺度，並具有極佳均勻性。也因為成長過程被侷限在陶瓷基板表面，在具有結構的表面上也能得到很好的覆蓋率與均勻性。The Atomic Layer Deposition (ALD) process is a common technique that mainly involves reacting a chemical gas containing the components to be deposited with a ceramic substrate, then removing the chemical gas with a large amount of inert gas (such as nitrogen or argon), and then repeating the above steps. This allows all reactions to occur only on the surface of the ceramic substrate, and each cycle only forms a thin film with a thickness of one atom. As a result, the accuracy of each film deposition thickness reaches the atomic level (about 0.1 nm) and has excellent uniformity. Because the growth process is confined to the surface of the ceramic substrate, good coverage and uniformity can be obtained on surfaces with structures.
請參閱第3圖所示，應用於固態電池之第二實施表面處理方法如下：
(1) 於該固體電解質層朝向該正極層及該負極層之表面，進行原子層蝕刻處理，用以進行表面處理301；
(2) 進行原子層沉積處理，於該固體電解質層與該正極層之間及該固體電解質層與該負極層之間，皆形成有一第一保護層及一第二保護層，該第一保護層之成份係為氧化鋁，而該第二保護層之成份係為氮氧化矽或氮化矽302。
Please refer to FIG. 3, the second implementation of the surface treatment method for solid-state batteries is as follows:
(1) Atomic layer etching is performed on the surface of the solid electrolyte layer facing the positive electrode layer and the negative electrode layer to perform
該固體電解質層13表面或/及正極層11表面上的缺陷，能夠先透過原子層蝕刻處理（Atomic Layer Etching, ALE）來移除細微表面缺陷（點缺陷Point defects、表面污垢Surface contamination、微刮痕microscratch，細粗糙(micro sharp-edgaed surface roughness)等）。Defects on the surface of the
該固體電解質層13與該正極層11之間，於該固體電解質層13朝向該正極層11之表面透過原子層蝕刻處理來移除表面缺陷。Between the
該固體電解質層13與該正極層11之間，於該正極層11朝向該固體電解質層13之表面透過原子層蝕刻處理來移除表面缺陷。Between the
該固體電解質層13與該正極層11之間，於該固體電解質層13朝向該正極層1之表面及該正極層11朝向該固體電解質層13之表面，透過原子層蝕刻處理來移除表面缺陷。Surface defects between the
該固體電解質層13表面或/及負極層12表面上的缺陷，能夠先透過原子層蝕刻處理（Atomic Layer Etching, ALE）來移除細微表面缺陷（點缺陷Point defects、表面污垢Surface contamination、微刮痕microscratch，細粗糙(micro sharp-edgaed surface roughness)等）。Defects on the surface of the
該固體電解質層13與該負極層12之間，於該固體電解質層13朝向該負極層12之表面透過原子層蝕刻處理來移除表面缺陷。Between the
該固體電解質層13與該負極層12之間，於該負極層12朝向該固體電解質層13之表面透過原子層蝕刻處理來移除表面缺陷。Between the
該固體電解質層13與該負極層12之間，於該固體電解質層13朝向該正極層1之表面及該負極層12朝向該固體電解質層13之表面，透過原子層蝕刻處理來移除表面缺陷。Between the
透過原子層沉積處理（Atomic Layer Deposition, ALD），如第4圖所示，將第一保護層111（成份係為氮氧化矽Al
2O
3）及第二保護層112（成份係為氮氧化矽SiO
xN
y或是Si
3N
4）沉積形成於該固體電解質層13與該正極層11之間，其中該第一保護層111係鄰近於固體電解質層13，而該第二保護層112係鄰近於正極層11。
By atomic layer deposition (ALD), as shown in FIG. 4 , a first protective layer 111 (composed of silicon oxynitride Al 2 O 3 ) and a second protective layer 112 (composed of silicon oxynitride SiO x N y or Si 3 N 4 ) are deposited between the
該原子層沉積處理（Atomic Layer Deposition, ALD）用以遮蓋較大表面缺陷（位錯Dislocations、微孔洞Microhole、微裂紋Microcracks等等）。The atomic layer deposition (ALD) process is used to cover larger surface defects (dislocations, microholes, microcracks, etc.).
上述原子層沉積處理，能夠先將第一保護層111沉積於該固體電解質層13朝向該正極層11之表面上，之後再將第二保護層112沉積於該第一保護層111上，該第二保護層112係介於該第一保護層111與該正極層11之間。The above atomic layer deposition process can first deposit the first
上述原子層沉積處理，亦能夠先將第二保護層112沉積於該正極層11朝向該固體電解質層13之表面上，之後再將該第一保護層111沉積於該第二保護層112上，該第一保護層111係介於該固體電解質層13與該第二保護層112之間。The above atomic layer deposition process can also first deposit the second
透過原子層沉積處理（Atomic Layer Deposition, ALD），如第4圖所示，將第一保護層121（成份係為氮氧化矽Al
2O
3）及第二保護層122（成份係為氮氧化矽SiO
xN
y或是Si
3N
4）沉積形成於該固體電解質層13與該負極層12之間，其中該第一保護層121係鄰近於固體電解質層13，而該第二保護層122係鄰近於負極層12。
By atomic layer deposition (ALD), as shown in FIG. 4 , a first protective layer 121 (composed of silicon oxynitride Al 2 O 3 ) and a second protective layer 122 (composed of silicon oxynitride SiO x N y or Si 3 N 4 ) are deposited between the
上述原子層沉積處理，能夠先將第一保護層121沉積於該固體電解質層13朝向該負極層12之表面上，之後再將第二保護層122沉積於該第一保護層121上，該第二保護層122係介於該第一保護層121與該負極層12之間。The above atomic layer deposition process can first deposit the first
上述原子層沉積處理，亦能夠先將第二保護層122沉積於該負極層12朝向該固體電解質層13之表面上，之後再將該第一保護層121沉積於該第二保護層122上，該第一保護層121係介於該固體電解質層13與該第二保護層122之間。The above atomic layer deposition process can also first deposit the second
該第一保護層111與該第二保護層112之總和厚度係小於10nm。The total thickness of the first
該第一保護層121與該第二保護層122之總和厚度係小於10nm。The total thickness of the first
本發明所提供之應用於固態電池之固體電解質和電極介面處理方法，與其他習用技術相互比較時，其優點如下： (1) 本案透過原子層蝕刻處理（Atomic Layer Etching, ALE），對固體電解質層表面或電極層（正極層或/及負極層）表面進行原子層蝕刻處理，以進行移除表面缺陷，如此能夠減少大型鋰凸（Dendride）形成，進而降低正副極短路之問題。 (2) 本案於初步表面處理後，再以原子層沉積處理（Atomic Layer Deposition, ALD）將表面缺陷遮蓋，將保護層沉積形成於該固體電解質層與該電極層（正極層、負極層）之間，如此亦能夠減少大型鋰凸（Dendride）形成。 (3) 本案之技術能夠減少大型鋰凸（Dendride）形成，故能夠降低正副極短路之問題，如此將能夠提高電池可靠度與使用壽命。 The solid electrolyte and electrode interface treatment method provided by the present invention for solid-state batteries has the following advantages when compared with other conventional technologies: (1) This case uses atomic layer etching (ALE) to perform atomic layer etching on the surface of the solid electrolyte layer or the surface of the electrode layer (positive electrode layer and/or negative electrode layer) to remove surface defects, thereby reducing the formation of large lithium protrusions (dendride) and thereby reducing the problem of short circuit between the positive and negative electrodes. (2) After the initial surface treatment, this case uses atomic layer deposition (ALD) to cover the surface defects and deposit a protective layer between the solid electrolyte layer and the electrode layer (positive electrode layer, negative electrode layer), which can also reduce the formation of large lithium protrusions (dendride). (3) The technology of this case can reduce the formation of large lithium protrusions (dendride), so it can reduce the problem of short circuit between the positive and negative electrodes, which will improve the reliability and service life of the battery.
本發明已透過上述之實施例揭露如上，然其並非用以限定本發明，任何熟悉此一技術領域具有通常知識者，在瞭解本發明前述的技術特徵及實施例，並在不脫離本發明之精神和範圍內，當可作些許之更動與潤飾，因此本發明之專利保護範圍須視本說明書所附之請求項所界定者為準。The present invention has been disclosed as above through the above-mentioned embodiments, but they are not used to limit the present invention. Anyone familiar with this technical field and having common knowledge can make some changes and modifications without departing from the spirit and scope of the present invention after understanding the above-mentioned technical features and embodiments of the present invention. Therefore, the scope of patent protection of the present invention shall be determined by the definition of the claim items attached to this specification.
1:固態電池1:Solid-state battery
11:正極層11: Positive layer
111:第一保護層111: First protective layer
112:第二保護層112: Second protective layer
12:負極層12: Negative layer
121:第一保護層121: First protective layer
122:第二保護層122: Second protective layer
13:固體電解質層13: Solid electrolyte layer
[第1圖] 係本發明應用於固態電池之固體電解質和電極介面處理方法之第一實施製備流程示意圖。 [第2圖] 係本發明應用於固態電池之固體電解質和電極介面處理方法之第一實施之固態電池結構示意圖。 [第3圖] 係本發明應用於固態電池之固體電解質和電極介面處理方法之第二實施製備流程示意圖。 [第4圖] 係本發明應用於固態電池之固體電解質和電極介面處理方法之第二實施之固態電池結構示意圖。 [Figure 1] is a schematic diagram of the preparation process of the first embodiment of the solid electrolyte and electrode interface treatment method for solid batteries of the present invention. [Figure 2] is a schematic diagram of the solid battery structure of the first embodiment of the solid electrolyte and electrode interface treatment method for solid batteries of the present invention. [Figure 3] is a schematic diagram of the preparation process of the second embodiment of the solid electrolyte and electrode interface treatment method for solid batteries of the present invention. [Figure 4] is a schematic diagram of the solid battery structure of the second embodiment of the solid electrolyte and electrode interface treatment method for solid batteries of the present invention.
Claims (7)
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| TW112106326A TWI848579B (en) | 2023-02-21 | 2023-02-21 | Solid electrolyte and electrode surface processing method for solid state battery |
| CN202410146425.7A CN118538993A (en) | 2023-02-21 | 2024-02-01 | Solid electrolyte and electrode interface processing method applied to solid-state battery |
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|---|---|---|---|---|
| CN107851840A (en) * | 2015-06-01 | 2018-03-27 | 气动覆层科技有责任限公司 | The manufacture method of battery for the nanometer engineering coating of active material of positive electrode, active material of cathode and solid electrolyte and comprising nanometer engineering coating |
| CN108736061A (en) * | 2017-04-21 | 2018-11-02 | 通用汽车环球科技运作有限责任公司 | Include the high-energy-density alkalinous metal battery of solid electrolyte |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107851840A (en) * | 2015-06-01 | 2018-03-27 | 气动覆层科技有责任限公司 | The manufacture method of battery for the nanometer engineering coating of active material of positive electrode, active material of cathode and solid electrolyte and comprising nanometer engineering coating |
| CN108736061A (en) * | 2017-04-21 | 2018-11-02 | 通用汽车环球科技运作有限责任公司 | Include the high-energy-density alkalinous metal battery of solid electrolyte |
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