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Journal of Materials Chemistry AMaterials for energy and sustainabilitywww.rsc.org/MaterialsA

ISSN 2050-7488

Volume 4 Number 1 7 January 2016 Pages 1–330

PAPERKun Chang, Zhaorong Chang et al. Bubble-template-assisted synthesis of hollow fullerene-like MoS

2 nanocages as a lithium ion battery anode material

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Controllable synthesis of LiFePO4 in different polymorphs and study of reaction mechanism

Hua Guoa,b,#

, He Pinga,#

, Jiangtao Hua, Xiaohe Song

a, Jiaxin Zheng

a, Feng Pan

a,*

Lithium Iron Phosphate, a widely used cathode material in Lithium Ion Batteries (LIB), crystalizes typically in olivine-type

phase, α-LiFePO4 (aLFP). However, the new phase β-LiFePO4 (bLFP) which can be transformed from aLFP under high

temperature with high pressure, can be produced through simple liquid-phase reaction. The mechanism of controllable

synthesis of the two polymorphs of lithium iron phosphate has not been studied thoroughly. In this paper, with thorough

experiments, we demonstrate that controllable synthesis of LFP with different crystal polymorphs can be obtained by

controlling certain conditions. Phosphate acid ratio in reactants and reaction time play key roles in the controllable

syntheses. Higher phosphate acid ratio and shorter reaction time would result in more bLFP content, while less phosphate

acid and longer reaction time would be beneficial to aLFP formation. To illustrate the mechanism for this phenomenon,

detailed reaction process was researched via X-ray diffraction, from which a possible mechanism associated with evolution

of crystal structures was demonstrated. Solvent content is also important for the process: some water content would lead

to nanoplate-shaped aLFP particles appearing. Their influence on the reaction could be attributed to change of

thermodynamics and kinetics, which leads to different crystal nucleation, growth and phase-change process.

Introduction

Olivine phase Lithium Iron Phosphate1 (LiFePO4, abbreviated

aLFP) has been a quite popular cathode material of Lithium Ion

Batteries (LIB) for its low cost, safety and proper

electrochemical property in ambient environment2, which has

been widely used for large-scale energy storage facilities and

electric vehicles (EV)3. But there are many shortcomings of

aLFP that limits its use in mobile phones, such as low electronic

conductivity and lithium migration efficiency4-9

, which can be

overcome by proper coating10

, ion-doping11

and nano-sizing12-

17. Lithium storage could also be extended by certain

treatment with the formation of certain interface18

.

Manufacture of aLFP is usually conducted in solid-calcine or

carbon-reduction method19

, products aLFP of which are made

in high temperature and suffers from uneven distribution in

size and quality. Nano-sized and well-shaped aLFP particles

could be synthesized by methods in liquid-state, like

hydrothermal or solvothermal method17

. But liquid-state

synthesis methods usually proceed in relatively low

temperature, in which aLFP was made from crystal growth20

.

The crystal growth process was not entirely clear even after

several articles21

exhibit the mechanism of aLFP crystal growth.

It is commonly accepted that hydrated ferrous phosphate

would appear as intermediate because of lower solubility

compared to lithium phosphate in water, which would react

further and produce aLFP with even lower solubility in

hydrothermal condition. While research22

showed a different

intermediate appeared during a reaction starting from ferrous

oxalate in ethanol glycol, which shows similar structure as

aLFP, and changed into aLFP in further reaction, showing

different mechanism of reaction because of reactants and

solvents. On the other hand, it is common acknowledged23

that an amorphous layer forms after hydrothermal or

solvothermal treatment, which shows lower lithium ion

migration efficiency24

compared to aLFP, and decreases during

the process then disappears after calcination, while using

ethanol glycol (EG) as solvent would reduce the crystal defects

efficiently12, 25

.

Beta Lithium Iron Phosphate (abbreviated bLFP) is another

morphology of LFP, in space group of Cmcm, which was found

in 200126

and could only be synthesized with high pressure at

an early stage27

. Liquid synthesis methods in ambient

atmosphere and low temperature of bLFP were reported only

after 201228

, using reactants similar to the ones used for

olivine phase product, with unique solvents as the key for the

controllable synthesis. In some of the research17

about aLFP,

bLFP would appear as an intermediate product during the

reaction, mechanism and influence of which are not

understood properly. Manthiram et al. reported29

the

synthesis of LiMPO4 (M=Mn, Fe, Co and Ni) in the crystal

polymorph of Cmcm, finding out that with proper reaction

condition, bLMP can be synthesized with a facile microwave-

assisted method, which leads to wonder about the key for

controllable synthesis of bLFP and aLFP, which are very

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ARTICLE Journal Name

2 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 20xx



important for LFP crystal research and manufacture in large

scale. Considering that product bLFP can be calcined and

changed into aLFP in short time, which can be conducted

during carbon coating and calcination procedure30

, with similar

process time, leading to final products of aLFP with less

defects20, 31

, compared with traditional synthesis procedure.

Research based on the use of bLFP as cathode material of

Lithium-ion has been conducted a lot, mostly focused on the

phase transformation to products in other phases with great

electrochemical properties through calcination32

, or defects

introduction33

. As shown in Figure S1, bLFP particles show little

capacity, which would increase to around 100 mAh/g after

introduced defects or annealed into aLFP, and would further

increase to 160 mAh/g if annealed into aLFP with carbon

coating. More importantly, aLFP with olivine-like structure

shows relatively unstable properties when exposed to air34, 35

,

which makes it difficult for the storage and transportation

under ambient condition (oxygen and humidity would result in

decomposition of aLFP), so usually aLFP should be coated with

thin carbon layer to prevent oxidation or composition

change36

. While bLFP suffers from its low lithium migration

properties37

, making it relatively more difficult to be

delithiated and oxidized (electrochemical properties shown in

Figure S1), which could make the manufacturing process easier

and cheaper, helpful for extent application of the material.

With more and more use of wet-chemical manufacture in

synthesizing LFP, more importance has been drawn into

research about solvothermal synthesis of LFP in different

conditions, which could affect the defects content, particle

morphologies and even crystal polymorphs of products. So it is

very important to study the mechanism and phase evolution

during solvothermal process in LFP synthesis. In this work, LFP

in different crystal polymorphs was synthesized with a facile

solvothermal method, with products controlled by different

aspects. Mechanism of the controllable synthesis was studied,

which would illustrate the process of LFP nucleation and

growth, and find out the key factor for controllable synthesis.

Experimental Methods

Synthesis method of LFP in different morphologies. All

reactants were used as bought without further treatment.

Ferrous sulfate, phosphate acid and lithium hydroxide, in a

ratio of 1: x: 2.7 (x = 1, 1.3, 1.5 and 1.8, products of which

named P1, P1.3, P1.5 and P1.8 respectively), were solute in

ethanol glycol (EG) separately. Ferrous sulfate and phosphate

acid solutions were mixed together first. Then lithium hydrate

solution was added slowly. After continuous stirring for 2 h,

produced gel-like mix was transferred into a Teflon-protected

autoclave inside a sealed stainless steel container and heated

to 180 oC for different time. This whole system was protected

by nitrogen atmosphere. Products were washed by water and

alcohol repeatedly right after cooled to room temperature,

dried in 80 oC vacuum oven overnight

30.

In the experiment of alternative adding sequence, lithium

hydroxide and phosphate acid were add together first, then

ferrous sulfate solution was added into the mixture under

continuous stirring, with other process same as steps

described.

Characterization of product powder. X-ray Diffraction (XRD)

was carried out with a Bruker D8-Advantage powder

diffractometer, of which light source was Cu-Kα radiation.

Scanning Electron Microscopy (SEM, carried out with ZEISS

SURPA 55) was applied to test morphology of the samples.

Differential Scanning Calorimetry (DSC, METTLER TOLEDO) was

applied to test heat flow change during the phase change.

Results and Discussion

Structure and morphology. Lithium Iron Phosphate with

different phases (aLFP and bLFP) was successfully synthesized

by solvothermal method (Figure 1), illustrated by XRD tests.

Particles of aLFP exhibit nanoplate morphology, with size of

about 300×500×30 nm3. The size and morphology are both

uniformly distributed, and every a few particles gathered in

parallelism forming a secondary particle. Particles of bLFP are

in form of nanorods with size of about 20×20×120 nm3,

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Journal Name ARTICLE




hundreds of which gather together end-to-end extending out

from center and form spherical secondary particles with

diameter of about 8 μm, as shown in Figure 1(b, e).

In Figure 1c, XRD result of aLFP is in strict consist of standard

sample result (PDF#40-1499) with no other peaks, meaning

that the acquired material is pure aLFP with no impurity. Same

for bLFP in accord with calculated peaks position from the

structure32

. Through detailed refinement with TOPAS software,

size distribution and crystal lattice parameters of statistic

results (as shown in Table S1) are similar with SEM results and

standard samples.

Influence of acid ratio. In the controllable synthesis process,

in order to obtain products with different polymorphs, acid

ratio in reactants was adjusted. When adjusting phosphate

acid ratio n (mole ratio of phosphate acid to ferrous ion being

n, with lithium hydroxide ratio being 2.7) increased from 1.0 to

2.0 (with pH adjusting from near neutral to lower), gathered

experiment product named Pn, and products changed from

aLFP to bLFP gradually, as shown in XRD results in Figure 2a. As

shown in Figure 2(b-e) respectively, shape of produced

particles changed from nanoparticles to nanorods for sample

P1.3, then to mixing of nanorods and smaller nanoparticles for

sample P1.5, finally becoming spheres consisting of nanorods

attaching to each other in P1.8. It is obvious combined with

XRD results that aLFP particles are in shape of nanoparticles

and then nanorods, while bLFP particles are in shape of

nanorods gathering into spheres, which can be explained by

mechanism of oriented attachment38

.

Influence of reaction time. Whereas in P1.8 experiment, it is

clearly shown that products changed from bLFP to aLFP when

solvothermal reaction time increased. Some content (18.7,

30.8, 60.1 and 81.5 %) of aLFP was obtained for different

reaction time (3, 7, 12 and 21 days respectively), as shown in

Figure 3a. It was obvious that aLFP content increased nearly

linearly to reaction time, as shown in Figure 3b, which was in

accordance with reaction course. The reason bLFP turned into

aLFP was that aLFP was more thermodynamically stable in the

condition, which was illustrated by former reports24

. From

some of the mixed production, morphology of certain particles

(Figure S2) showed strange combination of aLFP and bLFP

particles staggered, illustrating that aLFP was obtained by

dissolving of bLFP and recrystallizing into aLFP, as explained by

some similar papers21

. To further illustrate the argument, a

thermal test was carried (as shown in Figure S3), showing that

only from temperature of about 600 oC can bLFP be

transferred into aLFP under calcination condition, and DSC test

result showed that about 30 J/g of heat was released from the

system during the phase change. Calculation result of reaction

rate observed was much lower than calculated from Gibbs free

energy for same change in 180 oC - proves that direct phase

change from bLFP to aLFP was not the true process for the

reaction, and only dissolution-recrystallization process can

explain such low reaction rate under the

hydrothermal/solvothermal condition39

. (Detailed calculation

was shown in Supplementary Information S1.)

Mechanism for Controllable Synthesis. To illustrate the

mechanism behind different products in different acid ratio,

more detailed tests were conducted to verify the product

structure change during heating process in different

temperature for P1.3 and P1.5 experiments. It is obvious that

during initial crystallization state (around 100 oC), both aLFP

and bLFP nucleation were formed. But when heated to higher

temperature, XRD peaks of aLFP increase and peaks of bLFP

decrease, as labeled in Figure 3(c-d). P1.5 productions are pure

aLFP for 140 oC or 180

oC (different from previous

solvothermal product of aLFP and bLFP mixing, which could be

resulted from the slight difference in heat proved by Figure

S4). In order to make sure the crystal formation temperature

for products of different phases, detailed synthesis process

was tested. As shown in Figure S5, the obtained material was

first crystalized in form of bLFP in about 100 oC, and continued

crystallization process when the temperature was maintained,

illustrated by peaks heightening and sharpening shown in

Figure S5a. When system was heated to 180 oC, almost all

Figure 2. (a) XRD results for products with different phosphate acid ratio (ranging from 1.0 to 2.0), and SEM images showing different particle morphology produced by

different reactant ratio: phosphate acid ratios x is (b) 1, (c) 1.3, (d) 1.5 and (e) 1.8.


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product was pure aLFP, and remains after heating for 6 h as

shown in Figure S5b, illustrating that aLFP is a very stable form

under the condition.

To explain the reason that bLFP can only be formed in lower

pH environment, reaction mechanism of synthesis process

must be taken into account. First ferrous sulfate was mixed

with phosphate acid, which was source of acid atmosphere.

Then lithium hydroxide was added drop by drop into the

system, reacting with phosphate acid and turning the system

from acid to neutral atmosphere. The original ratio of ferrous

sulfate, phosphate acid and lithium hydroxide was 1: n: 2.7,

produced lithium phosphate precipitating which reacts with

iron immediately and forms amorphous intermediate, and it

has been certificated by experiments. When increasing

phosphate acid ratio, some of the intermediate product

changes from lithium phosphate (Li3PO4) to acidic phosphate

ion (H2PO4-), which was soluble in ethanol glycol, showing less

precipitation being gathered.

In order to explain the mechanism of different product’s

phases in different condition when first crystalized, structures

of lithium phosphate was compared with aLFP shown in Figure

S6 and Table S3. It is clearly shown that some similarity in

space group and similar lattice parameters lies behind the

controllable synthesis. The structure of lithium phosphate is

very similar to the one of aLFP, making the transforming

process more likely through an amorphous phase in which

lithium and ferrous ion co-precipitating with phosphate anion.

While in a system with more phosphate acid and thus lower

pH, the lithium and ferrous ion would dissolve into the ethanol

glycol solvent, instead of precipitating. Dissolved dihydrogen

phosphate and ferrous ion would form a certain structure with

lithium ion, making it easier to form bLFP when crystalized. In

order to prove the assumption, an additional experiment was

carried out, in which the system was heated before lithium

hydroxide was added. It turned out that crystallized

Fe7H4(PO4)6 appeared from the heating (XRD result shown in

Fig. S7), which can react with LiOH later and form bLFP, the

morphology of which in Fig. S8 clearly showed that LiOH from

solution reacted with Fe7H4(PO4)6 bulk particles in micrometer

size and became nano particles gathering together. The

similarity in these two crystal structures lies in form of

combination of Fe-O octahedral: Fe-O octahedral in both

crystal structure linked with each other with a shared edge,

which offers us the conclusion that ferrous oxygen octahedral

would be linked to other through shared edges in the solvent

environment. Thus in heating process, Lithium Phosphate

resulted from higher pH reacting with ferrous solution would

form aLFP preferentially, and in lower pH ferrous hydrogen

phosphate would form seed crystal of bLFP. Then after the first

crystallization, crystal growth and phase change would happen

Figure 3. XRD results of (a) P1.8 in different reaction states, with (b) content analysis. And detailed reaction process (crystallization process) monitor with

XRD for reactions (c) P1.3 and (d) P1.5.


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at the same time, with aLFP remaining and bLFP changing into

aLFP gradually. To further prove the assumption, experiments

with different adding sequence of raw materials were carried:

Lithium hydroxyl and phosphate acid were mixed first,

followed by adding ferrous sulfate drop by drop. It turns out

that similar phenomenon appeared in the system. With

phosphate acid ratio below 2.7, experiment were confirmed to

be aLFP, from relatively more-precipitation-existing precursor.

As shown in Fig. S8, bLFP only can form in a system with more

phosphate acid ratio of 2.7, which showed less precipitation

existing. More importantly, a combination of aLFP and bLFP

was produced from the experiment with phosphate acid ratio

of 2.7, which means that ratio of lithium hydroxyl and

phosphate acid ratio was 1:1, forming H2PO4- instead of PO4

3-

(Li3PO4), resulting in less precipitation in the precursor, and

proved the mechanism illustrated above. In normal adding

sequence, ferric ion could react with phosphate ion before

adding of lithium and heating, while in the new experiment,

phosphate would have to react with lithium hydroxyl first, only

phosphate left able to react with ferric ion to form

intermediate phase and produce bLFP finally.

Solvent effects in the synthesis. To illustrate the effects of

solvents (ethanol glycol) in the reaction, water of different

content was added into the reaction system (P1.8). When

ethanol glycol was used as reaction solvent, bLFP was gathered

as production. When adding certain ratio of water (adjusting

from 0% to 10%) into the reaction system, some content of

aLFP was produced, with content increasing from 0 to 100%,

shown as Figure 4(a-b) and Table S4. Combined with previous

analyze, water content has a significant influence towards the

nucleating and growth of crystals. When water complexing on

the surface of crystal or precursor, the stable energy would be

Figure 4. (a) XRD results for products with different phosphate acid ratio (ranging from 1.0 to 2.0), and SEM images showing different particle morphology produced by

different reactant ratio: phosphate acid ratios x is (b) 1, (c) 1.3, (d) 1.5 and (e) 1.8.


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totally different from ethanol glycol environment, thus

resulting in different reaction process, and materials with

different polymorphs. As reported in previous paper40

, H2O

would complex on the surface of precursor with ethanol glycol,

forming a unique morphology of nanoplate with thickness of

only 1 or 2 crystal lattices as illustrated by Figure S7, which

probably results in products’ morphology of nanoplates (Figure

4). In order to prove the universality of the phenomenon,

similar experiments were carried out in experiment P1.5. A

reasonable hypothesis based on previous analyze is that water

content in solvent would lead to precipitation of Li3PO4, caused

by relatively smaller the solubility in water than in ethanol

glycol.

The controllable synthesis was actually based on adjusting

crystal nucleating, growth and phase-change, by adjusting

reactants, adding sequence, solvents and reaction time, which

could be explained by formation of certain intermediate

product.

Conclusions

In conclusion, bLFP can be obtained by controllable

synthesized, and the mechanism behind the phenomena was

illustrated by analyzation of reaction condition. To control the

polymorphs of produced lithium iron phosphate, acid ratio in

reactants and reaction time should be controlled strictly,

mechanism of which was controlling the crystal nucleation,

growth and phase-change process. Relatively less phosphate

acid, longer reaction time or some water content in solvent

would lead to precipitation of Li3PO4, which could lead to

production of aLFP, otherwise bLFP would be produced. This

paper showing the key parameters in manufacturing lithium

iron phosphate, combining with the application of lithium iron

phosphate as electrode of lithium ion batteries, would lead to

some great development of commercial manufacture of

electrode materials.

Acknowledgements

This work was financially supported by National Materials

Genome Project (2016YFB0700600), the National Natural Science

Foundation of China (No. 21603007 and 51672012), and Shenzhen

Science and Technology Research Grant (No.

JCYJ20150729111733470, JCYJ20151015162256516).

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Illustrate 1. Mechanism for controllable solvothermal synthesis of LFP in different polymorphs.


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Table of Contents

Controllable synthesis of LiFePO4 with different crystal polymorphs can be obtained by

controlling certain conditions.


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