WO 2007/000251 PCT/EP2006/005725
Crystalline nanometric LiFePO4
The present invention relates to lithium secondary batteries and more specifically to
positive electrode materials operating at potentials greater than 2.8 V vs. Li+/Li in non-
aqueous electrochemical cells. In particular, the invention relates to crystalline nanometric
carbon-free olivine-type LiFePO4 powders with enhanced electrochemical properties, made
by a direct precipitation method.
Lithium secondary batteries are widely used in consumer electronics. They benefit from
the light weight of Li and from its strong reducing character, thus providing the highest
power and energy density among known rechargeable battery systems. Lithium secondary
batteries are of various configurations, depending on the nature of the electrode materials
and of the electrolyte used.
Current commercial Li-ion systems typically use LiCoO2 and carbon graphite as positive
and negative electrodes respectively, with LiPF6 in EC/DEC/PC as a liquid electrolyte. The
theoretical voltage of the battery is related to the difference between thermodynamic free
energies of the electrochemical reactions at the negative and positive electrodes. Solid
oxidants are therefore required at the positive electrode. The materials of choice, up to
now, are either the layered LiMO2 oxides (with M is Co, Ni and/or Mn), or the 3-
dimensionnal spinel structure of LiMn2O4. De-insertion of Li from each of these oxides is
concomitant with the M3+ into M4+ oxidation, occurring between 3.5 and 5 V vs. Li+/Li.
In US 5,910,382, three-dimensional framework structures using (XO4)n- polyanions have
been proposed as viable alternatives to the LiMxOy oxides. Among these compounds,
olivine-type LiFePCM appears to be the best candidate, since the Fe3+/Fe2+ potential is
located at an attractive value of 3.5 V vs. Li+/Li. Pioneering work of Padhi at al., J.
Electrochem. Soc, 144(4) (1997), 1188, demonstrated the reversible extraction/insertion of
Li+ ions from the olivine-type LiFePC4 prepared by a solid state reaction at 800 °C under
Ar atmosphere, starting from Li2CO3 or LiOH.H2O, Fe(II) acetate and NH4H2PO4.H2O. Due
mainly to electrical limitations, the capacity of the active material was only 60 to 70% of
CONFIRMATION COPY

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the theoretical capacity, which is 171 mAh/g, whatever the charge or discharge rate
applied. It is indeed known that the use of high synthesis temperatures (i.e. above 700 °C)
leads to the formation of large particles, in which ionic and electronic conductivity is a
limiting factor.
More recent work has been devoted to eliminate the electronic conductivity limitation.
This can be achieved by coating the LiFePO4 particles with a conducting phase. Besides
the basic physical techniques such as ball-milling of LiFePO4 with carbon black as
disclosed in WO 02/099913, other synthesis routes consist in forming carbon-coated
LiFePO4 by annealing an intimate mixture of the precursors and a carbon source, as is
disclosed in EP 1184920 and US 6,855,273. More complex methods were also developed,
in which LiFePCU and a surrounding conductive carbon coating were simultaneously
formed, for example in Huang et al., Electrochem. Solid State Lett., 4(10), A170-A172
(2001), and WO 2004/001881.
Nevertheless, despite all these improvements, two important problems remain unsolved
regarding the use of carbon-coated LiFePO4 in Li-ion batteries. The first one has been
described by Chen et al., in J. Electrochem. Soc, 149 (2002), Al 184, where it was shown
that the presence of carbon in the LiFePO4 powder had a dramatic impact on the tap
density of the powder, the latter being reduced by a factor 2 with only 2 wt.% carbon in the
carbon-coated LiFePO4, thereby leading to energy densities which are only half of those of
standard materials such as LiCOO2.
The second problem has been raised by Striebel et al. in J. Electrochem. Soc, 152 (2005),
A664-A670, where a compilation of tests of various carbon-coated LiFePO4 compounds
was published. The author insists on the fact that, even if the matrix conductivity has been
improved by coating, the battery developer would welcome so-far inexistent compounds
having a primary particle size in the 50 to 100 run range and, overall, attempts should be
made to minimise the particle size distribution, in order to yield better power efficiency. In
addition, Delacourt et al. in J. Electrochem. Soc, 152 (2005), A913-A921, demonstrated
that the conductivity of LiFePO4 was mainly of electronic nature, which led to the

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conclusion that the main electrical limitation of this compound is due to the Li+ ion
transport mechanism.
These recently published results emphasise the need for a carbon-free material, which does
not exhibit the above cited problems, and which has a reduced primary particle size in
order to shorten Li+ diffusion lengths and ohmic drop, as well as a narrow size distribution,
in order to ensure a homogeneous current distribution in the electrode and thus achieve
better battery performances, i.e. a high power efficiency and a long cycle life.
In order to produce fine carbon-free LiFePO4, ceramic synthesis methods, based on the
physical mixing of the precursors, have to be avoided, as they lead to micron-sized
powders which do not give any significant capacity at high rates, as was shown by Padhi et
al., in J. Electrochem. Soc, 144(4) (1997), 1188, and Yamada et al., J. Electrochem. Soc,
148 (3) (2001), A224. An alternative consists in dissolving the Li, Fe and P precursors in
an aqueous solution, followed by the formation of an amorphous Li/Fe/P mixture by water
evaporation. This dry precipitate is further heat-treated at around 500 to 700 °C for
crystallisation of the LiFePO4, as is disclosed in WO 02/27824 and EP 1379468. This
alternative method allows making submicron particles in the 0.5 to 1 µm range, but the
particle size distribution is so broad that these powders are not suitable for use as such in
batteries.
The best results so far have been obtained by hydrothermal synthesis, as reported by Yang
et al., in Electrochem. Comm., 3, 505-508 (2001). Reference is also made to JP2004-
095385A1. In this synthesis, the particle size as well as the particle size distribution (psd)
is largely dependent on the process used: Franger et al., in J. Power Sources, 119-121, 252-
257 (2003) and WO 2004/056702, developed a process leading to particles in the 1-20 µm
range, while Nuspl et al. presented in Proceedings of the IMLB 12 Meeting, Nara, Japan,
June 2004, ISBN 1-56677-415-2, Abs. 293, an optimised hydrothermal technique yielding
a carbon-free powder with a narrow particle size distribution and an average particle size
in the 400 to 600 tun range, and no particles above 1.3µm. Although useable without any

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carbon coating at low discharge rates, the particle size is still far away from the 50 to 200
nm range that is needed for adequate in-battery performance at high rates.
It is therefore the objective of this invention to disclose a novel process yielding metal
phosphate powders which offer essential improvements over the materials cited above.
To this end, a process is provided for preparing crystalline LiFePO4 powder, comprising
the steps of:
- providing a water-based mixture having at a pH between 6 and 10, containing a water-
miscible boiling point elevation additive, and Li(l), Fe(ll) and P(V) as precursor components;
- heating said water-based mixture to a temperature less than or equal to its boiling point at
atmospheric pressure, thereby precipitating the LiFePO4 powder.
At least part of the Li(l) can be introduced as LiOH, while at least part of the P(V) can be
introduced as H3PO4. The correct pH can usefully be reached by adjusting the ratio of
H3PO4 to LiOH. The obtained LiFePO4 powder can advantageously be heated it in non-
oxidising conditions, at a temperature below 600 °C, preferably above 200 °C and more
preferably above 300 °C.
The atmospheric boiling point of the water-based mixture is preferably above 100 °C and
below 200 °C, and more preferably from 105 to 120 °C. Use is made of a water-miscible
additive as a co-solvent. Useful co-solvents should have a boiling point higher than 100 °C
at atmospheric pressure. Ethylene glycol, diethylene glycol, N-methyl formamide,
dimethyl formamide, hexamethyl phosphoric triamide, propylene carbonate and
tetramethyl sulfone are appropriate examples; dimethyl sulfoxide (DMSO) is particularly
well suited. It is however difficult to find co-solvents allowing stable operation at
temperatures above 120 °C, let alone above 200 °C.
The invention also concerns a carbon-free crystalline LiFePO4 powder for use as electrode
material in a battery, having a particle size distribution with an average particle size d50
below 200 nm, and preferably above 50 nm. The maximum particle size is advantageously

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below 500 nm and the particle size distribution mono-modal with a ratio (d90-d10)/d50 of
less than 0.8, preferably less than 0.65, and more preferably less than 0.5.
In another embodiment, the use of a carbon-free crystalline LiFePO4 powder for the
manufacture of a lithium insertion-type electrode, by mixing said powder with a
conductive carbon-bearing additive, is disclosed, and the corresponding electrode mixture
is claimed.
When dealing with electrode mixtures for secondary lithium-batteries with non-aqueous
liquid electrolyte, the mix may comprise at least 90% by weight of the invented LiFePO4,
and is then characterised by a reversible capacity of at least 80%, and preferably at least 85
% of the theoretical capacity, when used as an active component in a cathode which is
cycled between 2.70 and 4.15 V vs. Li+/Li at a discharge rate of 1 C at 25 °C. The amount
of additives (binder and carbon) in the electrode mixture can be limited to less than 10%
because the mixture, being pasted on a current collector, needs not to be self-supporting for
this type of batteries.
When dealing with electrode mixtures for secondary lithium-batteries with non-aqueous
gel-like polymer electrolyte, the mix may comprise at least 80% by weight of the invented
LiFePO4, and is then characterised by a reversible capacity of at least 80%, and preferably
at least 85 % of the theoretical capacity, when used as an active component in a cathode
which is cycled between 2.70 and 4.15 V vs. Li+/Li at a discharge rate of 1 C at 25 °C. The
amount of additives in the electrode mixture can be as high as 20% in this case, because
the mixture, being rolled in the form of a sheet to be laminated to a current collector, needs
to be self-supporting during assembly of this type of batteries. However, in case of lithium-
batteries with non-aqueous dry polymer electrolyte, the mix may comprise at least 56% by
weight of the invented LiFePO4 as dry polymer electrolyte enters directly in the
composition of the electrode material.

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The details of the invention are illustrated by the following figures:
Fig. 1: XRD (Cu Kα) diagram of the as-obtained precipitate after 1 hour reaction time
under boiling conditions at 108 to 110 °C.
Fig. 2: SEM picture of the product of the invention.
Fig. 3: Volumetric particle size distribution (% vs. nm) obtained from image analysis on
SEM pictures of the product of the invention.
Fig. 4: Specific capacity relative to the active material as a function of the discharge rate
(mAh/g vs. C) for the Li/LiPF6 EC :DMC/LiFePO4 system. A: using the invented product;
B: according to prior art.
The fact that the precipitated particles are of nanometric size accounts for the excellent
high-drain properties of the batteries. This allows omitting carbon coating, a mandatory
step in the manufacture of all presently available powders if they are to be usefully
incorporated in a battery. The omission of carbon coating permits a significant increase of
the active material content of the electrode.
The particularly narrow particle size distribution facilitates the electrode manufacturing
process and ensures a homogeneous current distribution within the battery. This is
especially important at high discharge rates, where finer particles would get depleted more
rapidly than coarser particles, a phenomenon leading to the eventual deterioration of the
particles and to the fading of the battery capacity upon use.
Carbon-free crystalline nanometric LiFePO4 powder, with particles in the 50 to 200 nm
range and a very narrow particle size distribution may thus be obtained directly from
solution at atmospheric pressure by choosing appropriate working temperatures and pH.
Thermodynamic calculations have shown that Li3PO4 and Fe3(PO4)2.xH2O coexist at
temperatures up to 100 °C. However, by heating the solution above this temperature, and
preferably at or above 105 °C, the chemical equilibrium is shifted towards the formation of
pure LiFePO4: Li3PO4 + Fe3(PO4)2.xH2O → 3 LiFePO4+ x H2O. For this to occur, the pH
should be between 6.0 and 10.0, and preferably between 7.0 and 7.5.

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It is interesting to note that well crystallised pure LiFePO4 is already obtained after less
than one hour at 108 to 110 °C, as shown in Fig. 1. This indicates that nucleation and
growth are very fast, which accounts for the nanometric size of the particles obtained. A
longer residence time may further improve the crystallinity.
It is well-known that nanometric SiO2 or Al2O3 particles can be added to a solution in
order to act as nuclei for the precipitation of crystals. This could facilitate the nucleation
of the LiFePO4 with respect to the present invention. Also known is that adding surfactants
may help improve the dispersion of precipitates. This could prevent particle agglomeration
and may allow working with higher feed concentration with respect to the invented
LiFePO4 synthesis.
The obtained precipitate could contain traces or, occasionally, up to 15 to 20 at.% of Fe(III)
as confirmed by Mössbauer spectroscopy, and a small amount of hydroxyl groups, as
indicated by IR and TGA measurements. A short thermal treatment under slightly reducing
atmosphere above 200 °C may thus be advisable to enhance the purity of the LiFePO4
powder. Relatively mild conditions are useful so as to avoid grain growth or sintering: less
than 5 hours at a temperature below 600 °C is preferred. The resulting powder is shown in
Fig. 2. Noteworthy is that, as the crystalline triphylite LiFePO4 phase is already formed
during the precipitation step, the temperature and the dwell time of the thermal treatment
are significantly reduced compared to a ceramic synthesis process.
This invention is further illustrated in the following example.
Example
In a first step, DMSO is added to an equimolar aqueous solution of 0.1 M Fe(II) in
FeSO4.7H2O and 0.1 M P(V) in H3PO4, dissolved in H2O under stirring. The amount of
DMSO is adjusted in order to reach a global composition of 50 vol.% water and 50 vol.%
dimethyl sulfoxide.

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In a second step, an aqueous solution of 0.3 M LiOH.H2O is added to the solution at 25 °C,
in order to increase the pH up to a value comprised between 7 and 7.5. Hence, the final
Li:Fe:P molar ratio in the solution is close to 3:1:1.
In a third step, the temperature of the solution is increased up to the solvent's boiling point,
which is 108 to 110 °C, whereby LiFePO4 begins to precipitates. After one hour, the
precipitate is filtered and washed thoroughly with H2O.
A thermal treatment is finally performed by putting the dry precipitate at 500 °C for 3
hours in a slightly reducing N2/H2 (95/5) gas flow.
The volumetric particle size distribution of the product was measured using image
analysis. As shown in Fig. 3, the d50 value is about 140 nm, while the relative span,
defined as (d90-d10)/d50, is about 0.50.
A slurry was prepared by mixing 95% of the invented LiFePO4 powder with 5 wt.% of
ketjen carbon black and N-methyl-2-pyrrolidone (NMP) and deposited on an aluminium
current collector. The obtained electrode was used to manufacture coin cells, using a
loading of 3 mg/cm2 active material. Fig. 4 shows that an excellent discharge capacity is
maintained up to at least a discharge rate of 5C (curve A). The capacity at 1 C is 151
mA/g, corresponding to 88 % of the theoretical capacity of LiFePO4. As a comparative
example, results as reported by Nuspl et al. (curve B) show a lower overall reversible
capacity and higher losses, especially at rates above 1 C, even though only 79% of active
material was used in the electrode mixture, together with a loading of only 2.3 mg/cm .
The lower active material content and the lower loading indeed tend to give an upward bias
to the measured reversible capacity.
The capacity retention using the invented product proved also excellent, as no significant
degradation was apparent after 200 charge-discharge cycles at C/2 and at 5C. The capacity
of the cells indeed appeared to fade by less than 0.04% per cycle in the above discharge
conditions, a performance deemed to be on par with the current industrial demand.

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Claims
1. A process for preparing crystalline LiFePO4 powder, comprising the steps of:
- providing a water-based mixture having at a pH between 6 and 10, containing a water-
miscible boiling point elevation additive, and Li(I), Fe(II) and P(V) as precursor components;
- heating said water-based mixture to a temperature less than or equal to its boiling point at
atmospheric pressure, thereby precipitating the LiFePO4 powder.

2. A process according to claim 1, wherein at least part of the Li(I) is introduced as LiOH.
3. A process according to claim 1, wherein at least part of the P(V) is introduced as H3PO4.
4. A process according to claims 2 and 3, wherein the pH of the water-based mixture is
obtained by adjusting the ratio of LiOH to H3PO4.
5. Process according to any one of claims 1 to 4, followed by a step of post-treatment of
the LiFePO4 powder by heating it in non-oxidising conditions.
6. Process according to any one of claims 1 to 5, characterised in that the atmospheric
boiling point of the water-based mixture is above 100 and below 200 °C, and preferably
from 105 to 120 °C.
7. Process according to any one of claims 1 to 6, characterised in that the water-miscible
boiling point elevation additive is dimethyl sulfoxide.
8. Process according to any one of claims 1 to 7, characterised in that the step of post
treatment of the LiFePO4 is performed at a temperature below 600 °C, and preferably
above 200 °C.

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9. A carbon-free crystalline LiFePO4 powder for use as electrode material in a battery,
having a particle size distribution with an average particle size d50 below 200 nm, and
preferably above 50 nm.
10. A LiFePO4 powder according to claim 9, characterised in that the maximum particle
size is below 500 nm.
11. A LiFePO4 powder according to claims 9 or 10, characterised in that the particle size
distribution is mono-modal and in that the ratio (d90-dl0)/d50 is less than 0.8, preferably
less than 0.65, and more preferably less than 0.5.
12. Use of the carbon-free LiFePO4 powder according to any one of claims 9 to 11 for the
manufacture of a lithium insertion-type electrode, by mixing said powder with a
conductive carbon-bearing additive.
13. An electrode mix comprising the LiFePO4 powder according to any one of claims 9 to
12.
14. An electrode mix for secondary lithium-batteries with non-aqueous liquid electrolyte,
in particular according to claim 13, comprising at least 90% by weight of LiFePO4,
characterised by a reversible capacity of at least 80%, and preferably at least 85 % of the
theoretical capacity, when used as an active component in a cathode which is cycled
between 2.70 and 4.15 V vs. Li+/Li at a discharge rate of 1 C at 25 °C.
15. An electrode mix for secondary lithium-batteries with non-aqueous gel-like polymer
electrolyte, in particular according to claim 13, comprising at least 80% by weight of
LiFePO4, characterised by a reversible capacity of at least 80%, and preferably at least 85
% of the theoretical capacity, when used as an active component in a cathode which is
cycled between 2.70 and 4.15 V vs. Li+/Li at a discharge rate of 1 C at 25 °C.

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16. An electrode mix for secondary lithium-batteries with non-aqueous dry polymer
electrolyte, in particular according to claim 13, comprising at least 56% by weight of
LiFePO4, characterised by a reversible capacity of at least 80%, and preferably at least 85
% of the theoretical capacity, when used as an active component in a cathode which is
cycled between 2.70 and 4.15 V vs. Li+/Li at a discharge rate of 1 C at 25 °C.

The present invention relates to lithium secondary batteries and more specifically to positive electrode materials operating at potentials greater than 2.8 V vs. Li+ /Li in nonaqueous electrochemical cells. In particular, the invention relates to crystalline nanometric carbon- free olivine-type LiFePO4 powders with enhanced electrochemical properties. A direct precipitation process is described for preparing crystalline LiFePO4powder, comprising the steps of: - providing a water-based mixture having at a
pH between 6 and 10, containing a water -miscible boiling point elevation additive, and Li(I) , Fe(II) and P(V) as precursor components; -
heating said water-based mixture to a temperature less than or equal to its boiling point at atmospheric pressure, thereby precipitating crystalline LiFePO4 powder. An extremely fine 50 to 200 nm particle size is obtained, with a narrow distribution. The fine particle size accounts for excellent high-drain properties without applying any carbon coating. This allows for a significant increase in
the active material content of the electrode. The narrow distribution facilitates the electrode manufacturing process and ensures a
homogeneous current distribution within the battery.