Lithium borohydride

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Lithium borohydride

Unit cell of lithium borohydride at room temperature

Names

IUPAC name

Lithium tetrahydridoborate(1–)

Other names

Lithium hydroborate,

Lithium tetrahydroborate

Borate(1-), tetrahydro-, lithium, lithium boranate

 Identifiers

CAS Number  16949-15-8 

3D model (JSmol)  Interactive image

ChemSpider  55732 

ECHA InfoCard 100.037.277 

PubChem CID  4148881

RTECS number  ED2725000

UNII  8L87X4S4KP 

CompTox  DTXSID40895058 
Dashboard (EPA)

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InChI

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SMILES

Properties

Chemical formula LiBH4

Molar mass 21.784 g/mol

Appearance White solid

Density 0.666 g/cm3[1]

Melting point 268 °C (514 °F; 541 K)

Boiling point 380 °C (716 °F; 653 K) decomposes

Solubility in water reacts

Solubility in ether 2.5 g/100 mL

Structure[2]

Crystal structure orthorhombic

Point group Pnma

Lattice constant a = 7.17858(4), b = 4.43686(2), c = 6.80321(4)

 Lattice volume (V) 216.685(3) A3

Formula units (Z) 4

Coordination [4]B
geometry

Thermochemistry

Heat capacity (C) 82.6 J/mol K

Std molar 75.7 J/mol K

entropy (So298)

Std enthalpy of -198.83 kJ/mol

formation (ΔfH⦵298)

Hazards

Autoignition > 180 °C (356 °F; 453 K)

temperature

Except where otherwise noted, data are given for materials in

their standard state (at 25 °C [77 °F], 100 kPa).

 verify (what is   ?)

Infobox references

Lithium borohydride (LiBH4) is a borohydride and known in organic synthesis as

a reducing agent for esters. Although less common than the related sodium
borohydride, the lithium salt offers some advantages, being a stronger reducing agent
and highly soluble in ethers, whilst remaining safer to handle than lithium aluminium
hydride.[3]

Contents

 1Preparation
 2Reactions
o 2.1Chemoselectivity
o 2.2Hydrogen generation
 3Energy storage
 4See also
 5Notes
 6References

Preparation[edit]
Lithium borohydride may be prepared by the metathesis reaction which occurs upon
ball-milling the more commonly available sodium borohydride and lithium bromide:[4]
 NaBH4 + LiBr → NaBr + LiBH4
Alternatively it may be synthesized by treating boron
trifluoride with lithium hydride in diethyl ether:[5]
BF3 + 4 LiH → LiBH4 + 3 LiF

Reactions[edit]
Lithium borohydride is a stronger reducing agent
than sodium borohydride.[6] In mixtures
of methanol and diethyl ether, lithium borohydride is
able to reduce esters to alcohols
and primary amides to amines.[7] In contrast, these
substrates are unaffected by sodium borohydride. The
enhanced reactivity is attributed to the polarization of
the carbonyl substrate by complexation to the lithium
cation.[3]
Chemoselectivity[edit]
The use of lithium borohydride is particularly
advantageous in some preparations due to its
higher chemoselectivity relative to other popular
reducing agents such as lithium aluminium hydride. For
instance, unlike lithium aluminium hydride, lithium
borohydride will reduce esters, nitriles, lactones,
primary amides, and epoxides while sparing nitro
groups, carbamic acids, alkyl halides,
and secondary/tertiary amides.[7]
Hydrogen generation[edit]
Lithium borohydride reacts with water to produce
hydrogen. This reaction can be used for hydrogen
generation.[8]

Energy storage[edit]

Volumetric vs gravimetric energy density.

 Schematic of lithium borohydride recycling. Inputs are lithium
borate and hydrogen.

Lithium borohydride is renowned as one of the

highest energy density chemical energy carriers.
Although presently of no practical importance, the solid
will liberate 65 MJ/kg heat upon treatment with
atmospheric oxygen. Since it has a density of 0.67 g/cm3,
oxidation of liquid lithium borohydride gives 43 MJ/L. In
comparison, gasoline gives 44 MJ/kg (or 35 MJ/L),
while liquid hydrogen gives 120 MJ/kg (or 8.0 MJ/L). [nb
1]
 The high specific energy density of lithium borohydride
has made it an attractive candidate to propose for
automobile and rocket fuel, but despite the research
and advocacy it has not been used widely. As with all
chemical-hydride-based energy carriers, lithium
borohydride is very complex to recycle (i.e. recharge)
and therefore suffers from a low energy conversion
efficiency. While batteries such as lithium ion carry an
energy density of up to 0.72 MJ/kg and 2.0 MJ/L,
their DC to DC conversion efficiency can be as high as
90%.[9] In view of the complexity of recycling
mechanisms for metal hydrides,[10] such high energy
conversion efficiencies are not practical with present
technology.

Comparison of physical properties

Specific
Substance Density g/cm3 Energy density MJ/L
energy MJ/kg

LiBH4 65.2 0.666 43.4

Regular gasoline 44 0.72 34.8

Liquid hydrogen 120 0.0708 8

lithium ion
0.72 2.8 2
battery

See also[edit]
 Lithium aluminium hydride
 Sodium borohydride
 Direct borohydride fuel cell

Notes[edit]
1. ^ The greater ratio of energy density to specific
energy for hydrogen is because of the very low mass
density (0.071 g/cm3).

References[edit]
1. ^ Sigma-Aldrich Product Detail Page
2. ^ J-Ph. Soulie, G. Renaudin, R. Cerny, K. Yvon
(2002-11-18). "Lithium boro-hydride LiBH4: I. Crystal
structure".  Journal of Alloys and
Compounds.  346  (1–2): 200–
205.  doi:10.1016/S0925-8388(02)00521-2.
3. ^ Jump up to:a b Luca Banfi, Enrica Narisano, Renata
Riva, Ellen W. Baxter "Lithium Borohydride" e-EROS
Encyclopedia of Reagents for Organic Synthesis,
2001 John Wiley &
Sons. doi:10.1002/047084289X.rl061.pub2.
4. ^ Peter Rittmeyer, Ulrich Wietelmann "Hydrides" in
Ullmann's Encyclopedia of Industrial Chemistry,
2002, Wiley-VCH,
Weinheim. doi:10.1002/14356007.a13_199
5. ^ Brauer, Georg (1963). Handbook of Preparative
Inorganic Chemistry Vol. 1, 2nd Ed. New York:
Academic Press. p. 775.  ISBN  978-0121266011.
6. ^ Barrett, Anthony G.M. (1991). "Reduction of
Carboxylic Acid Derivatives to Alcohols, Ethers and
Amines". In Trost, Barry; Fleming, Ian; Schreiber,
Stuart (eds.). Reduction: Selectivity, Strategy &
Efficiency in Modern Organic Chemistry (1st ed.).
New York: Pergamon Press.
p. 244.  doi:10.1016/B978-0-08-052349-1.00226-2. I
SBN 9780080405995.
 7. ^ Jump up to:    Ookawa, Atsuhiro; Soai, Kenso (1986).
a b

"Mixed solvents containing methanol as useful

reaction media for unique chemoselective reductions
within lithium borohydride".  The Journal of Organic
Chemistry.  51  (21): 4000–
4005.  doi:10.1021/jo00371a017.
8. ^ Y. Kojima et al., "Hydrogen Generation by
Hydrolysis Reaction of Lithium Borohydride," 
International Journal of Hydrogen Energy,
29(12):1213-1217, August 2004; DOI:
10.1016/j.ijhydene.2003.12.009 sciencedirect link
9. ^ Valøen, Lars Ole and Shoesmith, Mark I. (2007).
The effect of PHEV and HEV duty cycles on battery
and battery pack performance (PDF). 2007 Plug-in
Highway Electric Vehicle Conference: Proceedings.
Retrieved 11 June 2010.
10. ^ US Patent 4002726 (1977) lithium borohydride
recycling from lithium borate via a methyl borate
intermediate

show

Lithium compounds (list)
Categories: 
 Borohydrides
 Lithium compounds
 Reducing agents
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Direct borohydride fuel cell

From Wikipedia, the free encyclopedia
Jump to navigationJump to search
Direct borohydride fuel cells (DBFCs) are a subcategory of alkaline fuel cells which
are directly fed by sodium borohydride or potassium borohydride as a fuel and either
air/oxygen[1] or hydrogen peroxide[2] as the oxidant. DBFCs are relatively new types of
fuel cells which are currently in the developmental stage and are attractive due to their
high operating potential in relation to other type of fuel cells. Recently, DBFCs that
rival proton-exchange membrane fuel cells (PEMFCs) in peak power but operating at
double the voltage have been reported.[3]

Contents

 1Chemistry
 2Advantages
 3Disadvantages
 4Cost
 5See also
 6References
 7External links

Chemistry[edit]
Sodium borohydride could potentially be used in more conventional hydrogen fuel
cell systems as a means of storing hydrogen. The hydrogen can be regenerated for a
fuel cell by catalytic decomposition of the borohydride:
NaBH4 + 2H2O → NaBO2 + 4H2
Direct borohydride fuel cells decompose and oxidize the
borohydride directly, side-stepping hydrogen
production and even producing slightly higher energy
yields:[4]
Cathode: 2O2 + 4H2O + 8e− → 8OH− (E0 = +0.4V)
Anode: NaBH4 + 8OH− → NaBO2 + 6H2O + 8e− (E0 =
-1.24 V)
Total E0 = +1.64V
The simplified reaction is:
NaBH4 + 2O2 → NaBO2 + 2H2O + Electricity
The working temperature of a direct sodium
borohydride fuel cell is 70 °C (158 °F).

Advantages[edit]
DBFCs could be produced more cheaply than a
traditional fuel cell because they do not need
expensive platinum catalysts. In addition, they
have a higher power density. The high operating
voltage of a DBFC reduces the number of cells
(in a series circuit) needed in a stack to achieve
a desired rated voltage and thus reduces the
stack costs considerably.[3]

Disadvantages[edit]
Unfortunately, DBFCs do produce some
hydrogen from a side reaction of NaBH4 with
water heated by the fuel cell. This hydrogen can
either be piped out to the exhaust or piped to a
conventional hydrogen fuel cell. Either fuel cell
will produce water, and the water can be
recycled to allow for higher concentrations of
NaBH4.
More importantly, the process of creating
electricity via a DBFC is not easily reversible.
For example, after sodium borohydride (NaBH 4)
has released its hydrogen and has been
oxidized, the product is NaBO2 (sodium
metaborate). Sodium metaborate might
be hydrogenated back into sodium borohydride
fuel by several different techniques, some of
which might theoretically require nothing more
than water and electricity or heat. However,
these techniques are still in active development.
As of June 30, 2010, many patents claiming to
effectively achieve the conversion of sodium
metaborate to sodium borohydride have been
investigated but none have been confirmed—the
current efficiency of "boron hydride recycling"
seems to be well below 1% which is unsuitable
for recharging a vehicle.[5]

Cost[edit]
Mass production projected prices for the fuel are
as low as US$5/kg, rivalling the cost of
hydrocarbon fuels. [6]

See also[edit]
 Glossary of fuel cell terms

References[edit]
1. ^ Amendola S.C., Onnerud P., Kelly M.,
Petillo P., Sharp-Goldman S. L and Binder
M. (1999) ‘A novel high power density
borohydride-air cell’, J. Power Sources, 84,
pp. 130–133.
2. ^ Choudhury, N.A.; Raman, R.K.; Sampath,
S.; Shukla, A.K. An alkaline direct
borohydride fuel cell with hydrogen
peroxide as oxidant. J. Power Sources
2005, 143, 1-8.
3. ^ Jump up to:a b Wang, Zhongyang; Parrondo,
Javier; He, Cheng; Sankarasubramanian,
Shrihari; Ramani, Vijay (April 2019).
"Efficient pH-gradient-enabled microscale
bipolar interfaces in direct borohydride fuel
cells".  Nature Energy. 4  (4): 281–
289.  Bibcode:2019NatEn...4..281W. doi:10
.1038/s41560-019-0330-5.  ISSN  2058-
7546.  S2CID 139154235.
4. ^ Ma, Choudhury, Sahai - A comprehensive
review of direct borohydride fuel cells
5. ^ Final Report: Electrochemical Hydrogen
Storage Systems, MacDonald 2010
6. ^ Suzanne w. Linehan; Arthur a. Chin;
Nathan t. Allen; Robert Butterick; Nathan t.
Kendall; i. Leo Klawiter; Francis j. Lipiecki;
Dean m. Millar; David c. Molzahn; Samuel
j. November; Puja Jain; Sara Nadeau; Scott
Mancroni (2010). "Low-Cost Precursors to
Novel Hydrogen Storage
Materials". doi:10.2172/1022594. OSTI 10
22594.

External links[edit]
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 Fuel cells

 Alkaline fuel cell

 Molten carbonate fuel cell

 Phosphoric acid fuel cell

 Proton-exchange membrane fuel cell

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 Direct-ethanol fuel cell

 Direct methanol fuel cell

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 Direct carbon fuel cell

 Zinc-air battery

 Metal hydride fuel cell

 Direct borohydride fuel cell

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