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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 217 records · Page 12

Influence of Borate on Sorption of Strontium and Barium to Calcium Silicate Hydrate - 20148

Radioactive waste with the decommissioning process at the Fukushima Daiichi Nuclear Power Plant (FDNPP), contains borate with relatively high concentration. As with general low-level wastes, such waste is also assumed the solidification with cementitious materials which calcium silicate hydrate (C-S-H) is one of the main components. In this study, the sorption behavior of strontium (Sr) ions and barium (Ba) ions to C-S-H in the presence of borate was examined by the sorption experiments without drying process. In the sorption experiments, C-S-H was synthesized by the mixture of calcium oxide, fumed silica and a solution with setting the Ca/Si molar ratios to 0.4, 0.8, 1.2 and 1.6. The total amount of a solid phase was 1.5 g, and the total volume of the solution containing borate and adsorbed ions (Sr or Ba) was 30 mL. The concentration of borate was set to 0 M or 0.6 M and the sodium/boron (Na/B) ratios was set to 0.2 or 1.0 by mixing boric acid and sodium hydroxide. The concentration of Sr ions or Ba ions was adjusted to 1 mM. The sorption period was set to 7 days. In the results, the sorption ratios of Sr ions and Ba ions for C-S-H exceeded 80% under all experimental conditions, although the sorption competition of cations with Na ions and the inhibition of the C-S-H formation with generating borate compounds observed by Raman spectroscopy might slightly reduce the sorption of them. These suggest that cationic radionuclides will be immobilized by C-S-H contained in the cements even in the presence of borate. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Revealing the roles of the solid–electrolyte interphase in designing stable, fast-charging, low-temperature Li-ion batteries

Designing the solid–electrolyte interphase (SEI) is critical for stable, fast-charging, low-temperature Li-ion batteries. Fostering a “fluorinated interphase,” SEI enriched with LiF, has become a popular design strategy. Although LiF possesses low Li-ion conductivity, many studies have reported favorable battery performance with fluorinated SEIs. Such a contradiction suggests that optimizing SEI must extend beyond chemical composition design to consider spatial distributions of different chemical species. In this work, we demonstrate that the impact of a fluorinated SEI on battery performance should be evaluated on a case-by-case basis. Sufficiently passivating the anode surface without impeding Li-ion transport is key. We reveal that a fluorinated SEI containing excessive and dense LiF severely impedes Li-ion transport. In contrast, a fluorinated SEI with well-dispersed LiF (i.e., small LiF aggregates well mixed with other SEI components) is advantageous, presumably due to the enhanced Li-ion transport across heterointerfaces between LiF and other SEI components. An electrolyte, 1 M LiPF 6 in 2-methyl tetrahydrofuran (2MeTHF), yields a fluorinated SEI with dispersed LiF. This electrolyte allows anodes of graphite, μSi/graphite composite, and pure Si to all deliver a stable Coulombic efficiency of 99.9% and excellent rate capability at low temperatures. Pouch cells containing layered cathodes also demonstrate impressive cycling stability over 1,000 cycles and exceptional rate capability down to −20 °C. Through experiments and theoretical modeling, we have identified a balanced SEI-based approach that achieves stable, fast-charging, low-temperature Li-ion batteries.

25 ENERGY STORAGE↗

Impacts of Lanthanum Impurities on Nickel-Rich Cathode Materials

The widespread use of lithium-ion batteries (LIBs) has led to environmental concerns and exacerbated the scarcity of essential minerals, underscoring the urgent need for effective recycling strategies. Among various recycling methods, the hydrometallurgical process is distinguished by its energy efficiency and minimal environmental impact. Nickel-metal hydride (Ni-MH) batteries are a significant source of nickel sulfate (NiSO 4 ) for hydrometallurgical recycling due to their substantial nickel content. A significant challenge arises from the effective separation of lanthanum (La), which results in at least 20 ppm of La being present in the recycled NiSO 4 . This study explores a critical aspect of the recycling process: the impact of La 3+ impurities, introduced through recycled NiSO 4 , on the performance of the synthesized nickel-rich cathode materials. We conducted a thorough investigation into how La 3+ influences morphology and structural integrity during both the synthesis of precursors and the production of cathode materials. Our findings indicate that La 3+ impurities do not adversely affect the morphology or structural integrity of the cathode precursors relative to virgin materials. However, higher concentrations of La 3+ reduce the discharge capacity with enhanced cycle stability by minimizing cation mixing between lithium (Li + ) and nickel (Ni 2+ ) ions within the cathode. Furthermore, this stability is crucial for extending battery life. Therefore, controlling the concentration of La 3+ impurities is essential for optimizing the electrochemical performance of recycled cathode materials.

Corrosion↗

Rapid charging made practical in graphite-based lithium batteries: surface-acoustic wave turbulent electrolyte mixing to overcome diffusion limited charging rates [Final Report]

One of the key limits in rapidly recharging a lithium-ion battery is the depletion of lithium ions within the electrolyte adjacent the anode during charging and long diffusion time to overcome this depletion. It also causes dendrite formation, inefficient use of the lithium, and battery degradation over many charge-discharge cycles. Because the liquid electrolyte remains quiescent and unmixed, this depletion layer’s depth rapidly grows to match the anode-cathode separation distance at even modest charge rates. The solution proposed by PI Prof. James Friend and Co-PI Prof. Ping Liu, both from the University of California, San Diego, is to mix the electrolyte and minimize the Li+ ion concentration gradient during charging. Even in the presence of the separator, the charging rate could then be significantly increased. They propose to accomplish this using surface acoustic wave (SAW)-driven acoustic streaming, a technique employing 10-mW fingernail-sized solid-state devices from the telecommunications industry to drive turbulent mixing to submicron length scales in a manner completely compatible with the typical 20700 and 18650 cells used in electric vehicles. 0.1. Turbulent acoustic streaming mixes the electrolyte during charging—even with separator Our proposed 100-MHz SAW device used to recirculate the electrolyte is compatible with lithium- ion battery electrochemistry, as it is made in our lab of single-crystal lithium niobate. Their solution is straightforward to drive from a DC power source alongside the signal provided during battery charging. The device is only needed during charging and does not consume power dur- ing battery discharge. Uniquely, SAW generates extreme accelerations of over 1 billion meters per second squared in the fluid, driving turbulent mixing from centimeter to submicron length scales, even through the porous separator materials that tend to be used in batteries, all while avoiding interfering with the anode’s solid electrolyte interphase layer that forms during use. By employing novel fluid mechanics, the investigators are proposing a new direction for battery research away from direct use of materials science and electrochemistry. The chemistry agnostic solution may be employed in any battery chemistry that makes use of liquid electrolytes, providing a broader transformative benefit to the battery research community. They are to produce a series of prismatic and 20700-cell sized 2 Ah batteries capable of being charged and discharged at least 500 times without more than 20% loss in battery capacity, and to provide analysis tools useful to the battery research and development community for adopting this approach for other battery chemistries and configurations.

25 ENERGY STORAGE↗

Steric Impediment of Ion Migration Contributes to Improved Operational Stability of Perovskite Solar Cells

The operational instability of perovskite solar cells (PSCs) is understood to mainly originate from the migration of ionic species (or charged defects) under a potential gradient. Compositional engineering of the “A” site cation of the ABX3 perovskite structure has been shown to be an effective route to improve the stability of PSCs. Here, the effect of size-mismatch-induced lattice distortions on the ion migration energetics and operational stability of PSCs is investigated. It is determined that the size mismatch of the mixed “A” site composition films and devices leads to a steric effect to impede the migration pathways of ions to increase the activation energy of ion migration, which is demonstrated through multiple theoretical and experimental evidence. Consequently, the mixed composition devices exhibit significantly improved thermal stability under continuous heating at 85 °C and operational stability under continuous 1 sun illumination, with an extrapolated lifetime of 2011 h, compared to the 222 h of the reference device.

14 SOLAR ENERGY↗

Molecular Engineering of Biorefining Lignin Waste for Solid-State Electrolyte

Lignin is the second most abundant renewable biopolymer on Earth but also a waste in both the paper industry and lignocellulosic biorefineries. Recently, lignin valorization has been extensively sought after to return economics, enhance carbon efficiency, and improve the bioeconomy, but the commercial value and size compatibility still hinder its applications. In this study, we developed a facile strategy to apply lignin waste into a solid-state electrolyte (SSE), which represents a safe next generation energy storage. Here, lignin was grafted with polyethylene glycol (PEG), an efficient lithium-ion (Li + ) conductive polymer, to enable its ion conduction. The synthesized PEG-g-lignin was mixed with poly(vinylidene fluoride)-co-hexafluoropropylene (PVDF-HFP) and PEG-g-lignin-based bis(trifluoromethanesulfonyl)imide (LiTFSI) to prepare a solid polymer electrolyte (SPE), which has an ionic conductivity of 2.5 × 10 –5 S/cm at 25 °C. This result was further enhanced to 6.5 × 10 –5 S/cm by adding an ion-conductive ceramic of Li 6.4 La 3 Ga 0.2 Zr 2 O 12 (LLGZO), which is referred to as composite polymer electrolyte (CPE). These data represent the highest ones among reported polymer-based SSE. A mechanistic study by using 2D HSQC NMR revealed that PEG-g-lignin has increased ether type β–O–4 linkages that can promote the interchain hopping of Li+ between lignin polymer chains, and 31 P NMR revealed that the lignin phenolic end can be associated by Li + . Moreover, the abundant aromatic moieties and methoxyl in PEG-g-lignin also enhanced Li + association and improved its ionic conductivity. The superior ionic conductivity of PEG-g-lignin-based SSE can enable massive applications of this biorefining waste in all-solid-state lithium batteries (ASSLBs), which has potential to promote the energy sector by promoting the bioeconomy and enhancing the renewability and sustainability of future energy storage.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Charge transport in mixed metal halide perovskite semiconductors

Investigation of the inherent field-driven charge transport behaviour of three-dimensional lead halide perovskites has largely remained challenging, owing to undesirable ionic migration effects near room temperature and dipolar disorder instabilities prevalent specifically in methylammonium-and-lead-based high-performing three-dimensional perovskite compositions. Here, in this paper, we address both these challenges and demonstrate that field-effect transistors based on methylammonium-free, mixed metal (Pb/Sn) perovskite compositions do not suffer from ion migration effects as notably as their pure-Pb counterparts and reliably exhibit hysteresis-free p-type transport with a mobility reaching 5.4 cm 2 V –1 s -1 . The reduced ion migration is visualized through photoluminescence microscopy under bias and is manifested as an activated temperature dependence of the field-effect mobility with a low activation energy (~48 meV) consistent with the presence of the shallow defects present in these materials. An understanding of the long-range electronic charge transport in these inherently doped mixed metal halide perovskites will contribute immensely towards high-performance optoelectronic devices.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Study of cluster ions produced from ToF-SIMS analysis of a U-6%Nb target

Cluster ions have been previously observed during time-of-flight secondary ion mass spectrometry (ToF-SIMS) analysis of metals and metal oxides. Furthermore, we have used ToF-SIMS to investigate cluster ions formed from the hydrocarbon-containing overlayer, the mixed U and Nb surface oxide, and underlying metal of a U-6 %Nb (U6Nb) target. In the overlayer, we observe U x O y + oxides and U-species likely containing hydrocarbons. In the surface oxide, we observe UO 2 +, U 2 O 2 +, U 3 O 5 +, and U 4 O 6 + as the most intense ions for each family of oxide ions containing x U atoms. Nb oxides for NbO 1-2 - were only observed in negative polarity. In contrast to the oxide, analysis of the underlying U6Nb alloy resulted in repeating units of U n +, U n (Nb)+, and U n (Nb 2 ) + ions for n = 3–11 as the highest intensity ions for each family of ions containing n U atoms. Nb n + clusters were not observed. U n +, U n (Nb)+, and U n (Nb 2 )+ clusters containing C- and O-species were observed and were likely produced from soluble C or O species or precipitates known to be present in U6Nb.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Valence Effects of Fe Impurity for Recovered LiNi 0.6 Co 0.2 Mn 0.2 O 2 Cathode Materials

Iron impurities are generally included in the obtained leaching liquor solution during the hydrometallurgical recycling method of spent lithium-ion batteries (LIBs) due to the usage of iron in battery casings and machinery parts of recycling equipment, which would definitely affect the physical and electrochemical features of the recovered active materials. In this paper, the effects of iron impurity with different valence states (Fe 2+ and Fe 3+ ) and gradient concentrations (0.2, 1.0, and 5.0 at. %) for the obtained LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NCM622) cathodes are fully studied. It is found that Fe3+ impurity could easily lower the tap density and average size of NCM622 particles and even introduce some impurity phases in the NCM622 structure at high concentration (5.0 at. %), leading to much lower specific capacity, worse rate capability, and cycling performance of the Fe 3+ -based NCM622 cathode. On contrast, with certain concentrations of Fe 2+ impurity (0.2 and 1.0 at. %), the NCM622 cathode material exhibits comparable and much better electrochemical properties compared with the virgin NCM622 materials. Based on these results, the valence of Fe impurity should be considered and controlled as well as its concentration during the recycling process design for spent LIBs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Photoinduced Anion Segregation in Mixed Halide Perovskites

Alloyed lead halide perovskites have taken a dominant role in the quest for third-generation solar cells. This is due to optimal light-harvesting properties, which can be tuned across the visible spectrum by mixing halide (X = Cl – , Br – , and I – ) anions and A + cations (A + = FA + , MA + , and Cs + ). Durability issues related to ion movement within the perovskite lattice, however, impede large-scale commercialization. Uniformly mixed halide perovskites [e.g., APb(I 1– x Br x ) 3 ] reversibly segregate into narrow bandgap I-rich and wide bandgap Br-rich domains during continuous visible illumination. Subsequent I-rich domains reduce local open circuit voltages and decrease mixed halide perovskite solar cell power conversion efficiencies. In this review, we assess the known effects of halide segregation on the structural and optical properties of mixed halide materials, discuss ongoing research to suppress the phenomenon, and finally provide a mechanistic overview of its underlying origins.

36 MATERIALS SCIENCE↗

Hyperstoichiometric Uranium Dioxides: Rapid Synthesis and Irradiation-Induced Structural Changes

Uranium dioxide (UO 2 ), the primary fuel for commercial nuclear reactors, incorporates excess oxygen forming a series of hyperstoichiometric oxides. Thin layers of these oxides, such as UO 2.12 , form readily on the fuel surface and influence its properties, performance, and potentially geologic disposal. This work reports a rapid and straightforward combustion process in uranyl nitrate–glycine–water solutions to prepare UO 2.12 nanomaterials and thin films. We also report on the investigation of the structural changes induced in the material by irradiation. Despite the simple processing aspects, the combustion synthesis of UO 2.12 has a sophisticated chemical mechanism involving several exothermic steps. Raman spectroscopy and single-crystal X-ray diffraction (XRD) measurements reveal the formation of a complex compound containing the uranyl moiety, glycine, H 2 O, and NO 3 – groups in reactive solutions and dried combustion precursors. Combustion diagnostic methods, gas-phase mass spectroscopy, differential scanning calorimetry (DSC), and extracted activation energies from DSC measurements show that the rate-limiting step of the process is the reaction of ammonia with nitrogen oxides formed from the decomposition of glycine and uranyl nitrate, respectively. However, the exothermic decomposition of the complex compound determines the maximum temperature of the process. In situ transmission electron microscopy (TEM) imaging and electron diffraction measurements show that the decomposition of the complex compound directly produces UO 2 . The incorporation of oxygen at the cooling stage of the combustion process is responsible for the formation of UO 2.12 . Spin coating of the solutions and brief annealing at 670 K allow the deposition of uniform films of UO 2.12 with thicknesses up to 300 nm on an aluminum substrate. Irradiation of films with Ar 2+ ions (1.7 MeV energy, a fluence of up to 1 × 10 17 ions/cm 2 ) shows unusual defect-simulated grain growth and enhanced chemical mixing of UO 2.12 with the substrate due to the high uranium ion diffusion in films. As a result, the method described in this work allows the preparation of actinide oxide targets for fundamental nuclear science research and studies associated with stockpile stewardship.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Halogen Redox Shuttle Explains Voltage-Induced Halide Redistribution in Mixed-Halide Perovskite Devices

Voltage-induced halide segregation greatly limits the optoelectronic applications of mixed-halide perovskite devices, but a mechanistic explanation behind this phenomenon remains unclear. In this work, we use electron microscopy and elemental mapping to directly measure the halide redistribution in mixed-halide perovskite solar cells with quasi-ion-impermeable contact layers under different bias polarities to find iodide and bromide accumulation at the cathode and anode, respectively. This is consistent with a mechanism based on preferential iodide oxidation at the anode, leading to unbalanced I$^{+}_{i}$, I$^{-}_{X}$, and Br$^{-}_{X}$ fluxes. Importantly, switching the anode from "inert" Au to "active" Ag prevents segregation because Ag oxidation precludes the oxidation of lattice iodide, which suggests employing redox-active additives as a general strategy to suppress halide segregation. Finally, these results show that halide perovskite devices operate as solid-state electrochemical cells when threshold voltages are exceeded, providing fresh insight to understand the impacts of voltage bias on halide perovskite devices.

14 SOLAR ENERGY↗

Simultaneously improved reversibility and hydrogen production of solid oxide cells through infiltrating air electrode

Among the various fuel cells, solid oxide cells (SOCs) are the unique type that can principally operate reversibly as either fuel cells to produce electricity or as an electrolyser to split water and produce green hydrogen (H 2 ). Nevertheless, the SOCs' reversibility presents enormous challenges that are manifested by the fast degradation through the cycling between fuel cell and electrolysis mode. While the La 0.8 Sr 0.2 MnO 3 /yttria-stabilized zirconia (LSM/YSZ) air electrode possesses significant advantages in terms of high electrical conductivity and high thermal stability under fuel cell mode, the SOCs with the LSM/YSZ air electrode experience rapid performance degradation with catastrophic electrode delamination shortly after switching from fuel cell to electrolysis mode. To prevent such catastrophic delamination and enable the electrolysis H 2 production, a chemical solution with the designed chemistry of SrFe 2 O 4-d was infiltrated into the LSM/YSZ air electrode. The infiltration immediately mitigates the catastrophic delamination, and the infiltrated cells exhibit significantly improved reversibility upon the electrochemical operation. Nanostructure examination reveals nanoscale cracks and second-phase nanograins formed in the air electrode from the baseline cell. By contrast, no delamination was observed at either the micron or the nanoscale for the infiltrated cell, which is attributed to the increased ion conductivity of the Fe-doped LSM mixed conductor induced by the significant interdiffusion between the LSM backbone and infiltrates. Here, this study presents a viable method for preventing electrode delamination while enhancing the durability of H 2 production and power generation for reversible fuel cell/electrolysis cell operation. It further opens new research directions of modifying the electrochemical activity of the electrode of inherently functional cells through the infiltration of the solutions with different chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Indium and thallium extraction into betainium bis(trifluoromethylsulfonyl)imide ionic liquid from aqueous hydrochloric acid media

The partitioning behavior of indium and thallium ions between aqueous hydrochloric acid solutions and hydrophobic betainium bis(trifluoromethylsulfonyl)imide ionic liquid was studied using a standard liquid–liquid extraction technique. The experiments were mainly carried out by means of a radiochemical method, using 111 In and 201 Tl medical radionuclides at an ultra-trace concentration. Both mono- and trivalent thallium were utilized and the highest oxidation state (3+) was produced by adding either chlorine or bromine water to the aqueous phase prior to extraction. The metal ion transfer was optimized by varying the aqueous concentration of hydrochloric acid and by introducing zwitterionic betaine as an extracting agent into the aqueous phase. It was found that the highest D values of In(III), Tl(III) and Tl(I) in the investigated chemical systems were up to 200, 70, and 1, respectively. The influence of the addition of lithium salt, having common with the ionic liquid counterion, and the variation of mixing time on the distribution ratio of the metal ions were also studied. Finally, to understand the underlying extraction mechanism of the metal ions and to propose the predominant extracted species, mathematical models based on ion pair formation and ion exchange were developed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Molecular Examination of Ion-Pair Competition in Alkaline Aluminate Solutions Using In Situ Liquid SIMS

Understanding the structure and composition of aluminate complexes in extremely alkaline systems such as Bayer liquors has received enormous attentions due to its fundamental and industrial importance. However, obtaining direct molecular information of the underlying ion-ion interactions using traditional approaches such as NMR or Raman spectroscopy is challenging due to the weakness of these interactions and/or their complex overlapping spectral signatures. Here, we exploit in situ liquid secondary ion mass spectrometry (SIMS) as a new approach and show how it enables new insights. In contrast with traditional techniques, using SIMS we succeeded in acquiring information on dominant ion clusters in these alkaline systems. In Na + /K + mixed alkaline aluminate solutions we clearly observe preferential formation of Na + -anion clusters over K + -anion clusters. Further, evaluation of these clusters by density functional theory (DFT) calculations shows that these structures are stable and that their relative bond energies are consistent with their observed SIMS signal intensity differences. This demonstrates a key advantage of in situ liquid SIMS for overcoming ambiguities obscuring important information in these systems on constituent molecular clusters defined by relatively weak ion pair competition and ion-solvent interactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Cesium exhibits different mesoscale segregation and ion pairing than lithium, sodium, or potassium in concentrated alkaline aqueous nitrite solutions

Understanding ion pairing in concentrated alkaline electrolytes facilitates the prediction and control of chemical processes in nuclear waste. While sodium is the dominant alkali metal in such systems, cesium often exhibits distinct bulk behavior relative to lighter alkali cations. Aqueous mixtures of cesium hydroxide and sodium nitrite were compared to alkali hydroxide analogs using small-angle x-ray scattering, revealing that cesium disrupts the sodium nitrite electrolyte structure, forming cesium-rich domains. This mesoscale segregation contrasts with the near-ideal mixing observed in other mixed hydroxide–nitrite systems. Raman spectroscopy indicates cesium–nitrite ion pairing, evidenced by vibrational shifts distinct from those associated with sodium. Multinuclear magnetic resonance spectroscopy further supports cesium–nitrite and cesium–hydroxide association, revealing a distinct local environment for nitrite in cesium-containing solutions. Together, these findings show that cesium promotes a unique solution structure dominated by specific ion pairing within segregated domains. This structural organization may influence radical generation pathways in high-ionic-strength alkaline media relevant to nuclear waste processing and management.

Nienhuis, Emily T. [Pacific Northwest National Lab↗

2D kinetic-ion simulations of inverted corona fusion targets

Laser-driven “inverted corona” fusion targets have attracted interest as a low-convergence neutron source and platform for studying kinetic physics. The scheme consists of a hollow or gas-filled spherical shell made of deuterated plastic. The shell has one or more laser entrance holes (LEH), resembling a spherical hohlraum. The laser passes through the LEH’s and illuminates the interior surface of the shell, ablating a plasma that travels inward towards the target center. Long ion mean free paths in the converging plasma can lead to significant interpenetration, atomic mix, and other kinetic effects. Here, in this work we report on numerical simulations of inverted corona targets using the kinetic-ion, fluid–electron hybrid particle-in-cell (PIC) approach in 2D RZ geometry. 2D simulations suggest that shape effects do not have a significant impact on plasma evolution and observed yield trends are primarily the result of 1D kinetic mix mechanisms. Simulations are also compared against available experimental data recorded at the OMEGA laser facility. In particular, synthetic x-ray emission images show good qualitative agreement with experimental results, albeit with an apparent timing discrepancy for the two-sided vacuum target. More generally, we demonstrate the potential of hybrid-PIC simulations for full-system modeling and experimental design, including collisional absorption of laser energy, plasma evolution, mix, and fusion burn.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗