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arxiv: 1907.09327 · v1 · pith:VUEXH6NJnew · submitted 2019-07-22 · ❄️ cond-mat.mtrl-sci · cond-mat.soft

Properties of LiMnBO3 glasses and nanostructured glass-ceramics

P.P. Michalski , A. Go{\l}\k{e}biewska , J. Tr\'ebosc , O. Lafon , T.K. Pietrzak , J. Ryl , J.L. Nowi\'nski , M. Wasiucionek
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J.E. Garbarczyk
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Pith reviewed 2026-05-24 18:07 UTC · model grok-4.3

classification ❄️ cond-mat.mtrl-sci cond-mat.soft
keywords LiMnBO3glass-ceramicselectrical conductivitynanocrystallizationgrain boundariessolid-state NMRlithium batteriesmelt quenching
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The pith

Thermal nanocrystallization of LiMnBO3 glass creates nanostructured glass-ceramics whose conductivity rises six orders of magnitude at room temperature.

A machine-rendered reading of the paper's core claim, the machinery that carries it, and where it could break.

The paper examines the thermal, structural and electrical properties of LiMnBO3 prepared first as a glass by melt quenching and then as a nanocrystallized glass-ceramics. The starting glass shows dc conductivity on the order of 10 to the minus 18 siemens per centimeter at room temperature and is dominated by ionic transport. Thermal nanocrystallization yields a nanostructured material containing both MnBO3 and LiMnBO3 crystalline phases. Conductivity in this glass-ceramics increases by six orders of magnitude relative to the parent glass. The authors link the gain to electronic transport that occurs along the newly formed grain boundaries, a value also higher than conductivities reported for other manganese- and borate-containing glasses.

Core claim

The thermal nanocrystallization of the glass produces a nanostructured glass-ceramics containing MnBO3 and LiMnBO3 phases. The electric conductivity of this glass-ceramics is increased by 6 orders of magnitude, compared to the starting material at room temperature. Such improved conductivity stems from the facilitated electronic transport along the grain boundaries.

What carries the argument

Nanostructured glass-ceramics containing MnBO3 and LiMnBO3 phases, whose grain boundaries enable electronic transport

If this is right

  • The conductivity of the nanostructured glass-ceramics exceeds values reported for other manganese- and borate-containing glasses in the literature.
  • The initial glass conductivity is dominated by ionic rather than electronic contributions.
  • SEM and 7Li solid-state NMR establish that the parent glass consists of two distinct glassy phases.
  • Nanocrystallization converts the low-conductivity glass into a higher-conductivity composite while preserving overall chemical composition.

Where Pith is reading between the lines

These are editorial extensions of the paper, not claims the author makes directly.

  • Testing the same nanocrystallization route on other borate compositions would show whether grain-boundary electronic transport is a general route to conductivity gains.
  • Varying the density of grain boundaries while holding phase fractions fixed would isolate their contribution from any effect of the new crystalline phases themselves.
  • If grain boundaries remain the dominant path, similar nanostructuring could be applied to related cathode or electrolyte compositions to improve room-temperature performance.
  • The two-phase glassy structure identified by NMR may itself influence how crystallization proceeds and where boundaries form.

Load-bearing premise

The six-order conductivity increase is caused by electronic transport along grain boundaries rather than by changes in phase composition, measurement geometry, or contact resistance.

What would settle it

A measurement that isolates electronic from ionic conductivity contributions in the glass-ceramics and shows that electronic transport does not account for the observed increase.

Figures

Figures reproduced from arXiv: 1907.09327 by A. Go{\l}\k{e}biewska, J.E. Garbarczyk, J.L. Nowi\'nski, J. Ryl, J. Tr\'ebosc, M. Wasiucionek, O. Lafon, P.P. Michalski, T.K. Pietrzak.

Figure 1
Figure 1. Figure 1: DTA curve for heating rate 10 °C.min–1 . Characteristic thermal events were marked with arrows. Tab. 1. Temperatures of characteristic thermal events for heating rates 10 °C.min–1 and 1 °C.min–1 . heating rate / °C.min–1 Tg / °C Tc1 / °C Tc2 / °C Tc3 / °C 10 424 484 550 589 1 411 506 568 XRD measurements XRD measurements were carried out at temperatures from RT up to 675 °C in order to investigate phases t… view at source ↗
Figure 2
Figure 2. Figure 2: XRD patterns as function of temperature for step-wise heating. h-LiMnBO3, m-LiMnBO3 and o-MnBO3 patterns are displayed as olive squares, red dots and blue triangles, respectively. LiBO2 peak is marked with diamond and LiAlSiO4 inclusions are marked with asterisks. We also collected diffractograms after isothermal annealing of 10 and 20 h at 525 °C. The temperature corresponds to that for which the diffract… view at source ↗
Figure 4
Figure 4. Figure 4: Arrhenius plot for electrical conductivity. Black dots stand for heating ramp of initial glass, colored dots [PITH_FULL_IMAGE:figures/full_fig_p007_4.png] view at source ↗
Figure 5
Figure 5. Figure 5: Impedance spectra at 200 °C of the initial glass (left) during the heating ramp and of a glass [PITH_FULL_IMAGE:figures/full_fig_p008_5.png] view at source ↗
Figure 7
Figure 7. Figure 7: SEM images of sample surface: a) glass; b [PITH_FULL_IMAGE:figures/full_fig_p009_7.png] view at source ↗
Figure 8
Figure 8. Figure 8: High-resolution XPS spectra for the glass (left) and for nanomaterial, after annealing at 500 °C (right). Comparing both spectra, one can see that the manganese signal for nanocrystallized sample is very low. As the XPS is the surface technique, this should be related to manganese diffusion from surface to inner layers, as the glass is annealed. The peaks positions were attributed to proper manganese valen… view at source ↗
Figure 9
Figure 9. Figure 9: Experimental (black line) and best-fit simulated (red line) 1D 7Li MAS NMR spectrum of the initial glass (black line) at 1.9 T with a MAS frequency of 30 kHz. The inset shows an expansion of the central transition. The simulated 7Li spectrum is the sum of two distinct lineshapes (displayed as olive lines in the inset) with parameters given [PITH_FULL_IMAGE:figures/full_fig_p011_9.png] view at source ↗
Figure 1
Figure 1. Figure 1: DTA curve for heating rate 10 °C.min–1 . Characteristic thermal events were marked with arrows [PITH_FULL_IMAGE:figures/full_fig_p016_1.png] view at source ↗
Figure 4
Figure 4. Figure 4: Arrhenius plot for electrical conductivity. Black dots stand for heating ramp of initial glass, [PITH_FULL_IMAGE:figures/full_fig_p016_4.png] view at source ↗
Figure 5
Figure 5. Figure 5: Impedance spectra at 200 °C of the initial glass (left) during the heating ramp and of a glass￾ceramics after nanocrystallization at 500 °C (right), during the cooling ramp [PITH_FULL_IMAGE:figures/full_fig_p017_5.png] view at source ↗
read the original abstract

Polycrystalline LiMnBO3 is a promising cathode material for Li-ion batteries. In this work, we investigated the thermal, structural and electrical properties of glassy and nanocrystallized materials having the same chemical composition. The original glass was obtained via a standard meltquenching method. SEM and 7Li solid-state NMR indicate that it contains a mixture of two distinct glassy phases. The results suggest that the electrical conductivity of the glass is dominated by the ionic one. The dc conductivity of initial glass was estimated to be in the order of 10-18 S.cm-1 at room temperature. The thermal nanocrystallization of the glass produces a nanostructured glass-ceramics containing MnBO3 and LiMnBO3 phases. The electric conductivity of this glass-ceramics is increased by 6 orders of magnitude, compared to the starting material at room temperature. Compared to other manganese and borate containing glasses reported in the literature, the conductivity of the nanostructured glass ceramics is higher than that of the previously reported glassy materials. Such improved conductivity stems from the facilitated electronic transport along the grain boundaries.

Editorial analysis

A structured set of objections, weighed in public.

Desk editor's note, referee report, simulated authors' rebuttal, and a circularity audit. Tearing a paper down is the easy half of reading it; the pith above is the substance, this is the friction.

Referee Report

2 major / 2 minor

Summary. The manuscript reports preparation of LiMnBO3 glass by melt-quenching, its characterization by SEM and 7Li solid-state NMR (indicating two glassy phases), and thermal nanocrystallization to produce a glass-ceramic containing MnBO3 and LiMnBO3 phases. The glass is stated to exhibit ionic-dominated dc conductivity of order 10^{-18} S cm^{-1} at room temperature; the glass-ceramic is reported to show a six-order-of-magnitude conductivity increase attributed to facilitated electronic transport along grain boundaries, exceeding values for previously reported Mn- and B-containing glasses.

Significance. If the conductivity enhancement and its mechanistic attribution are substantiated with appropriate controls, the result would be of interest for nanostructured cathode or electrolyte materials in Li-ion batteries, as it suggests a route to conductivity improvement via controlled nanocrystallization beyond typical glassy borates.

major comments (2)
  1. [Abstract] Abstract: the claim that the six-order conductivity increase 'stems from the facilitated electronic transport along the grain boundaries' is not supported by any reported data separating ionic and electronic contributions (e.g., transference numbers, Hebb-Wagner polarization, or impedance spectra showing distinct grain-boundary arcs). Without such evidence, the causal attribution cannot be distinguished from intrinsic conductivity of the new crystalline phases or changes in geometry/contact resistance.
  2. [Abstract] Abstract: the stated glass conductivity (~10^{-18} S cm^{-1}) and the magnitude of the increase are presented without error bars, raw impedance data, baseline measurements on the crystalline phases alone, or controls confirming that nanocrystallization did not alter electrode interfaces or effective sample dimensions.
minor comments (2)
  1. The abstract contains typographical inconsistencies ('meltquenching' instead of 'melt-quenching'; '10-18 S.cm-1' instead of standard scientific notation '10^{-18} S cm^{-1}').
  2. The statement that the glass-ceramic conductivity exceeds 'previously reported glassy materials' would be strengthened by explicit literature citations or a comparative table.

Simulated Author's Rebuttal

2 responses · 0 unresolved

We thank the referee for the careful review and constructive comments on our manuscript. We address each major comment below.

read point-by-point responses

  1. Referee: [Abstract] Abstract: the claim that the six-order conductivity increase 'stems from the facilitated electronic transport along the grain boundaries' is not supported by any reported data separating ionic and electronic contributions (e.g., transference numbers, Hebb-Wagner polarization, or impedance spectra showing distinct grain-boundary arcs). Without such evidence, the causal attribution cannot be distinguished from intrinsic conductivity of the new crystalline phases or changes in geometry/contact resistance.

    Authors: We agree that direct measurements separating ionic and electronic contributions (transference numbers or Hebb-Wagner polarization) were not performed. Our attribution relies on the observed six-order increase coinciding with grain-boundary formation in the glass-ceramic, the ionic character of the parent glass, and literature on the crystalline phases. We acknowledge this leaves room for alternative explanations such as intrinsic crystalline conductivity. In revision we will rephrase the abstract to present the grain-boundary mechanism as a proposed interpretation rather than a firmly established conclusion and will add a short discussion of possible alternatives. revision: partial

  2. Referee: [Abstract] Abstract: the stated glass conductivity (~10^{-18} S cm^{-1}) and the magnitude of the increase are presented without error bars, raw impedance data, baseline measurements on the crystalline phases alone, or controls confirming that nanocrystallization did not alter electrode interfaces or effective sample dimensions.

    Authors: The reported values are order-of-magnitude estimates from impedance spectroscopy. We accept that error bars, representative raw spectra, and explicit controls would strengthen the presentation. In the revised manuscript we will add representative impedance data (with uncertainty estimates where possible), clarify that measurements on the glass and glass-ceramic were performed under identical electrode and geometric conditions, and note that separate baseline measurements on phase-pure crystals were outside the scope of the present study. We will also acknowledge the possibility of interface or dimensional changes as a contributing factor. revision: yes

Circularity Check

0 steps flagged

No circularity: experimental measurements with no derivation chain or self-referential fitting

full rationale

This is a purely experimental materials science paper reporting synthesis, structural characterization (SEM, NMR), thermal analysis, and direct dc conductivity measurements on glass and nanocrystallized samples. Conductivity values (~10^{-18} S cm^{-1} for glass, ~10^{-12} S cm^{-1} for glass-ceramic) are presented as measured results, not derived from equations or fitted parameters that are then relabeled as predictions. The interpretation linking the increase to grain-boundary electronic transport is an inference from the data, not a self-definitional or self-citation-dependent step. No mathematical models, uniqueness theorems, ansatzes, or renamings of known results appear. The paper is self-contained against external benchmarks via reported experimental protocols and literature comparisons.

Axiom & Free-Parameter Ledger

0 free parameters · 0 axioms · 0 invented entities

No free parameters, axioms, or invented entities are identifiable from the abstract; the contribution is experimental characterization of thermal, structural, and electrical properties.

pith-pipeline@v0.9.0 · 5783 in / 1100 out tokens · 27091 ms · 2026-05-24T18:07:24.801723+00:00 · methodology

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Reference graph

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