Comments:

-Reviewer 1
- The manuscript deals with a study of the role of predominant facet for LiMn2O4 as it relates
to its electrochemical performance.

1) minor point - LiCoO2 (intro) is a pretty established cathode (rather than a potential
cathode)

‘Potential cathode’ is removed from the revised MS as suggested by the reviewer.

2) p3 "een" - word error

The word “een” is corrected to ‘even’ in the revised MS.

3) p4 Celgard (capital C)

The correction is appropriately incorporated in the revised MS.

4) does the manuscript follow the MRB format? It may but I just found it unusual that the
computation details seemed to be mixed into a short intro.

As indicated by the reviewer, the computational details and the experimental details are
dealt with under a separate section in the revised MS.

5) when I think of capping ligands I think of molecules (i.e. citric acid) that at a molecular
level cap a facet to alter growth - does graphene some how cap a face selectivity? Does
sit alter the solution growth somehow?

Exactly, this is an important finding made using the crystal shape algorithm. The
influence of graphene is not just to enhance the electrical conductivity of the material as
was thought earlier. Graphene, with its huge surface area, caps the thermodynamically
least stable (311) face. Crystal growth then occurs predominantly along the
thermodynamically more stable faces (400), (111) and (331). LiMn2O4 (CH_cap) therefore
acquires a cubic crystal habit and exhibits superior electrochemical performance (Fig. 4c)
compared to LiMn2O4 (CH) , with a hexagonal crystal habit, where the crystal growth is
along the (400), (111), (331) & (311) direction.

This paragraph is incorporated in the revised MS.

6) p7 How does a centrifuge/washing effort alter crystal growth? Whats the physical
difference between 3 and 7 washes?

It’s our experimental observation that the predominance of (311) plane is decreased with the
increase in centrifugal parameter, here the number of hydrothermal centrifuges. Thus
centrifugal force contributes to selective capping action and alters the crystal habit.

7) p6 is Mn loss driven by a facet based reaction of is it a chemical loss driven by Mn(III)

formation?

By Mn loss, here we mean the chemical loss due to Mn (III) dissolution in the electrolyte
during the operation of the lithium battery. The (311) phase is predominant in the
hexagonal crystal habit as compared to the cubic habit. In the atomic arrangement of the
(311) plane, Mn atoms are arranged close to the surface of the plane. This brings the Mn
atoms close to the electrochemical interface, in the lithium battery system, which thereby
increases the chance for reactions such as valence disproportionation and manganese
dissolution into the electrolyte. These reactions lead to loss of electrochemical capacity in
the lithium battery.

This paragraph is incorporated in the revised MS to improve the clarity.

8) what % of the materials had a hexagonal appearance - I know you said you could see one
in the SEM and agglomeration was an issue - but I assume the data may also give you an
idea how much hexagobal vs cubic appearance is present in the sample?

In a compound containing a mixture of crystal habits, the crystal shape algorithm can
only pick out an average information from which we can get an idea on the predominant
crystal habit. If one wants to extract the various percentages of the different crystal
habits, one has to recore several XRD’s in different orientations, and then carry out a
statistical analysis, which is beyond the scope of the present work.

9) does the washing selectively break down one of the two morphologies?

Yes. This question is elaborately answered in comment no. 6.

-Reviewer 2

-
This manuscript present a strong correlation between morphologies and electrochemical
performance of conventional LiMn2O4 cathode materials. Based on the experiments combined
with DFT calculations, a notable improvement in the electrochemical performance of LiMn2O4
has been well explained.

1. Authors claimed that the cubic crystal habit of LiMn2O4 shows much better
electrochemical performance as compared to the hexagonal crystal habit. It would also
affect rate capability of LiMn2O4 as well. Further confirmation is still required.
Yes, rate capability is also influenced by the crystal habit. We have added new figures to
demonstrate that cubic crystal habit (Fig. 4e) possesses better rate capability compared to
the hexagonal crystal habit (Fig. 4d).

2. The loading amount of active materials on the electrode and the density of electrode
would be important information to figure out the electrochemical performance of the
materials more clearly.

In this MS, wherever two crystal habits are compared, the loading amount of active
materials, the densification and all the other parameters were maintained a constant.

3. More clear SEM and TEM images should be provided to confirm the cubic crystal habit
and the hexagonal crystal habit of LiMn2O4.

The SEM and TEM images were already published in peer reviewed journals and are
reproduced in this short review, with permission. Presently we are out of the materials
characterization laboratory and it is immediately not possible to produce new SEM/TEM
images.