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3D打印陶瓷 3D 打印 SOFA 的研究現已擴展到 SPEC

2020-07-30  2839

諸如固體氧化物燃料和電解池之類的基于電陶瓷的能源設備有望成為受益于使用3D打印技術開發創新概念的候選人,這些概念克服了現有制造技術的形狀局限性。在2017年進行的一項類似項目的基礎上,《材料化學雜志》發表了一項新研究,報告了使用陶瓷立體光刻技術制造一系列新型高性能SOEC(電解質支持的固體氧化物電池)的過程。用氧化釔穩定的氧化鋯3D打印常規的平面和高縱橫比的波紋狀電解質,以制造固體氧化物電池。瓦楞紙設備在燃料電池和共電解模式下的性能提高了57%,與平面設備相比,其面積直接成比例。這種設計上的增強與印刷設備的經驗證的耐用性(小于35 mV / 1000 h)相結合,代表了該領域的一種全新方法,并有望對下一代固體氧化物電池以及更廣泛的固體電池產生巨大影響。狀態能量轉換或存儲設備。

Electroceramic-based energy devices like solid oxide fuel and electrolysis cells are promising candidates to benefit from using 3D printing to develop innovative concepts that overcome shape limitations of currently existing manufacturing techniques. Building on a similar project conducted in 2017, a new study published by the Journal of Material Chemistry, reports on the fabrication a new family of highly performing SOECs – electrolyte-supported solid oxide cells – using ceramics stereolithography. Conventional planar and high-aspect-ratio corrugated electrolytes were 3D printed with yttria-stabilized zirconia to fabricate solid oxide cells. Corrugated devices presented an increase of 57% in their performance in fuel cell and co-electrolysis modes, which is directly proportional to the area enlargement compared to the planar counterparts. This enhancement by design combined to the proved durability of the printed devices (less than 35 mV/1000 h) represents a radically new approach in the field and anticipates a strong impact in future generations of solid oxide cells and, more generally, in any solid-state energy conversion or storage devices.

固體氧化物燃料電池(SOFC)是零排放的發電機,能夠在整個千瓦范圍內以高于60%的效率(LHV)將氫轉化為電能。在熱電聯產(CHP)中,這種效率可以達到高達90%(LHV)的值,而SOFC是目前存在的最高效的能源生產設備之一。可替代地,以反向模式操作的相同裝置是能量存儲單元,其能夠從電和水產生可存儲的氫。 SOEC(固體氧化物電解槽)是一種高效的能量轉換裝置,與競爭性的電解技術相比,具有更高的產量和更低的比電能。

Solid oxide fuel cells (SOFCs) are zero-emission power generators able to convert hydrogen into electricity with efficiency (LHV) above 60% over the whole range of kilowatt scales. This efficiency can reach values as high as 90% (LHV) in combined heat and power units (CHP), with SOFCs being one of the most efficient energy generation devices currently existing. Alternatively, the same devices operated in reverse mode are energy storage units able to produce storable hydrogen from electricity and water. SOECs (solid oxide electrolysis cells) are highly efficient energy conversion devices, with higher production yields and lower specific electric energy than competing electrolysis technologies.

固體氧化物電池(SOC)是基于陶瓷的多層電化學電池,由在兩側均帶有電極的氣密性氧化物離子導體電解質組成。 SOC的最先進材料是用于電解質的氧化釔穩定氧化鋯(YSZ),并結合以YSZ為基礎的復合材料作為電極,即用于氧電極的鑭鍶錳礦(LSM-YSZ)和用于燃料的Ni-YSZ電極。

Solid oxide cells (SOCs) are ceramic-based multilayer electrochemical cells consisting of a gas-tight oxide-ionic conductor electrolyte with electrodes in both sides. The state of the art materials for SOCs are yttria-stabilized zirconia (YSZ) for the electrolyte, combined with YSZ-based composites as electrodes, namely, lanthanum strontium manganite (LSM-YSZ) for the oxygen electrode and Ni–YSZ for the fuel electrode.

由于可能通過制造復雜的陶瓷形狀而受到嚴格的限制,因此只有極少數的策略可以通過改變其幾何形狀來直接提高電池性能,而目前尚未開發出任何策略。例如,通過電解質的皺紋增加電池的有效面積將直接減小電池的內電阻,即其面積比電阻,從而按比例增加每個投影面積的性能。

Only few strategies have been explored to take advantage of a straightforward increase of the performance of the cells by modification of its geometry, likely due to the strict limitations in manufacturing complex ceramic shapes. For instance, an increase of the active area of the cells by corrugation of the electrolyte will directly reduce the internal resistance of the cell, i.e. its area-specific resistance, proportionally increasing their performance per projected area.

這項研究提出了通過具有波紋結構的SLA 3D打印制造250μm厚的8YSZ(8 mol%氧化釔穩定的氧化鋯)電解質,與同樣印刷的平面對應物相比,其本質上增加了約60%的有效面積。在這項工作中,在800-900°C的燃料電池溫度范圍以及CO2和蒸汽共電解模式下,對這兩種類型電池的電化學性能進行了全面表征。細胞阻抗譜的分析可以清楚地識別增強的起源。瓦楞紙架構在此作為可打印幾何形狀的第一個示例進行討論,可以通過這項工作中提出的陶瓷3D打印方法來制造瓦楞紙,證明了它在改善如此獲得的電池性能方面的不公平優勢。

This study presents the fabrication of 250 μm-thick 8YSZ (8 mol% yttria-stabilized zirconia) electrolytes by SLA 3D printing with a corrugated architecture, which intrinsically increases around 60% the active area compared to an also printed planar counterpart. A comprehensive characterization of the electrochemical performance of both types of cells is presented in this work in a range of temperatures between 800–900 °C in fuel cell and CO2and steam co-electrolysis modes. The analysis of the impedance spectroscopy of the cells allowed the clear identification of the origin of the enhancement. The corrugated architecture is discussed here as a first example of the wide range of printable geometries that can be fabricated by the ceramic 3D printing approach proposed in this work, proving its unfair advantage in improving the performance of the so obtained cell.

通過使用3DCERAM的陶瓷3D打印機CERAMAKER制造平面和波紋狀的YSZ陶瓷件。使用計算機輔助設計(CAD)軟件繪制直徑為2.00厘米(其中電極沉積的直徑為1.6厘米,確定電池的未來有效面積)且厚度為250μm的平面和波紋膜的草圖分別具有2.00和3.15 cm2的不同有效表面積。此類膜與外部環形環整體集成,以提高機械穩定性并在測試過程中確保膜的良好密封。

Planar and corrugated YSZ ceramic pieces were fabricated by using CERAMAKER a ceramic 3D printer from 3DCERAM. Computer Assisted Design (CAD) software was employed to sketch planar and corrugated membranes of the same 2.00 cm in diameter (of which 1.6 cm is the diameter for the electrode deposition, determining the future active area of the cell) and 250 μm in thickness but with different effective surface areas of 2.00 and 3.15 cm2, respectively. Such membranes were monolithically integrated with external annular rings to enhance the mechanical stability and ensure good sealing of the membranes during the testing.

為了在燒結后獲得此處所述的尺寸,應采用重新縮放工藝,以考慮燒結過程中的收縮(出于清晰原因,未報告初始設計值)。通過使用DMC軟件對設計進行切片并控制3D打印機,可以自動創建STL文件。使用由3DCERAM制成的3DMIX-8YSZ無溶劑紫外光固化漿料,該漿料由8YSZ陶瓷粉,丙烯酸酯紫外光固化單體,光引發劑和分散劑組成。用可光聚合的粘合劑替代溶劑可實現高陶瓷填充量,良好的均質性和較低的懸浮液粘度,可通過添加稀釋劑進一步改善。33沉積了具有高陶瓷填充量(約50 vol%)的8YSZ漿料在30×30 cm2的印刷平臺上通過雙刮刀系統能夠均勻地分散漿料。

To obtain the dimensions here described after the sintering, a rescaling process is applied to take into account the shrinkage during the sintering process (initial design values are not reported for clarity reasons). STL files were automatically created by using DMC software to slice the design and control the 3D printer. The 3DMIX-8YSZ solvent-free UV-photocurable slurry from 3DCERAM, which is composed by 8YSZ ceramic powder, acrylate UV curable monomer, photoinitiator and dispersant, was employed. The substitution of solvents by photo-polymerizable binders allows to achieve high ceramic loading, good homogeneity and a low viscosity of the suspension, which is further improved by adding diluents.33 8YSZ slurry with high ceramic loading (ca. 50 vol%) was deposited over a 30 × 30 cm2 printing platform by a double doctor blade system able to homogeneously spread the paste.

調節葉片以沉積厚度為25μm的薄層。在沉積可光固化漿料后,聚焦在建筑平臺上的UV半導體激光器(功率約500 mW)會逐片地復制由CAD設計的圖案,并使用鏡面光柵以5000 mm s-1的速度旋轉。在紫外線照射下,含有自由基和在紫外線區域具有活性的光引發劑34的可光固化漿料會在自由基光聚合過程后局部固化。

The blades were adjusted to deposit a thin layer of 25 μm in thickness. After deposition of the photocurable slurry, a UV semiconductor laser (power around 500 mW) focused at the building platform reproduces, slice by slice, the pattern designed by CAD using mirror rastering with a speed of 5000 mm s?1. Under UV exposure, the photocurable slurry, containing a monomer and a photoinitiator active in the UV region,34 locally solidifies following a free-radical photopolymerization process.

自立式3D打印的8YSZ膜的圖像。平面膜和波紋膜的俯視圖(a和b)和橫截面(c和d)。平面(e)和波紋(f)電解質的SEM橫截面詳細信息,(在插圖中)顯示了逐層3D打印過程定義的步驟。

Images of the self-standing 3D printed 8YSZ membranes. Top view (a and b) and cross-section (c and d) of the planar and corrugated membranes, respectively. Detail of the cross-section by SEM for the planar (e) and corrugated (f) electrolytes showing (in the inset) the steps defined with the layer-by-layer 3D printing process.

使用先前優化的標準程序制造對稱和完全電化學電池。將商用NiO–YSZ和LSM–YSZ漿料(美國燃料電池材料)涂在3D打印的YSZ片上,分別作為燃料和氧氣電極。燃料電極和氧電極分別使用1400°C的附著溫度3 h和1200°C的附著溫度1 h。

Symmetrical and full electrochemical cells were fabricated using previously optimized standard procedures. Commercial NiO–YSZ and LSM–YSZ pastes (Fuel cell materials, USA) were painted on 3D printed YSZ pieces as fuel and oxygen electrodes, respectively. Attachment temperatures of 1400 °C for 3 h and 1200 °C for 1 h  were employed for the fuel and oxygen electrodes, respectively.

高溫燒結后,通過SLA 3D打印制造了平面波紋狀8YSZ獨立式膜,從而獲得了無裂紋且均勻的零件。總體而言,3D打印的YSZ零件被認為適合在SOFC / SOEC應用中用作電解質。平面和波紋狀LSM-YSZ / YSZ / Ni-YSZ固體氧化物燃料電池的性能通過在800°C至900°C的溫度范圍內的氫氣(燃料電極)和合成空氣(氧氣電極)氣氛下測量極化曲線來評估℃。

Planar and corrugated 8YSZ freestanding membranes were fabricated by means of SLA 3D printing after sintering at high temperatures to obtain crack-free and homogeneous parts. Overall, the 3D printed YSZ parts are considered suitable for working as electrolytes in SOFC/SOEC applications. The performance of the planar and corrugated LSM–YSZ/YSZ/Ni–YSZ solid oxide fuel cells was evaluated by measuring polarization curves under hydrogen (fuel electrode) and synthetic air (oxygen electrode) atmospheres in the temperature range between 800 °C and 900 °C.

具有常規(平面)和增強區域(波紋)架構的電解質支持的固體氧化物電池已通過陶瓷3D打印技術成功制造。具有平面幾何形狀的3D打印固體氧化物電池在燃料電池和共電解模式下均表現出良好的性能(與常規電池相比)。更有趣的是,波紋狀細胞顯示出的改善與3D結構實現的活性面積的增加成正比。在這項工作中,與傳統的SOFC技術(LSM–YSZ / YSZ / Ni–YSZ)相比,直接提高了60%,在900°C時可獲得410 mW cm-2的出色最大功率密度。

Electrolyte-supported solid oxide cells with both conventional (planar) and enhanced-area (corrugated) architectures were successfully fabricated with ceramic 3D printing technologies. 3D printed solid oxide cells with planar geometry presented a good performance (comparable to conventional cells) in both fuel cell and co-electrolysis mode. More interestingly, corrugated cells showed an improvement directly proportional to the increase of their active area achieved by 3D structuration. In this work, a direct increase of 60% on conventional SOFC technology (LSM–YSZ/YSZ/Ni–YSZ) was reached obtaining an excellent maximum power density of 410 mW cm?2 at 900 °C.

類似地,在以共電解模式運行的波紋狀固體氧化物電解槽中注入了1.3 V時600 mA cm-2的高電流密度。此外,即使在高電流密度條件下(在850°C下j = 360 mW cm-2),經600小時持續時間的耐久性測試也證明了增強細胞的降解極低。這些優異的結果可以被認為是制造新一代固態氧化物電池的第一步,這種固態氧化物電池的性能與其從平面到三維的自然變化有關。此增強功能超出了其波紋電解質的高縱橫比,并且包括具有嵌入式功能和改進的可堆疊性的3D打印結構元素。這項工作的3D打印方法代表了一種通用的方法,可以增加高性能和耐用復雜設備的設計自由度,并且是能源行業增材制造革命的一步。

Similarly, a high current density of 600 mA cm?2 at 1.3 V was injected in a corrugated solid oxide electrolysis cell operating in co-electrolysis mode. Moreover, a remarkably low degradation of the enhanced cells was proved in durability tests of 600 h of duration even at high-current density conditions (j = 360 mW cm?2 at 850 °C). These exceptional results can be considered the first step for the fabrication of a radically new generation of solid oxide cells with enhanced performance related to their change in nature from planar to three-dimensional. This enhancement goes beyond the high-aspect-ratio of their corrugated electrolyte and includes 3D printed structural elements with embedded functionality and improved stackability. The 3D printing methodology of this work represents a versatile approach that increases the design freedom for high performing and durable complex devices and a step forward in the revolution of the additive manufacturing in the energy sector.

文章來源:3dprintingmedia



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