Research Article

Capturing metastable structures during high-rate cycling of LiFePO4 nanoparticle electrodes

Science  27 Jun 2014:
Vol. 344, Issue 6191,
DOI: 10.1126/science.1252817

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Structured Abstract

Introduction

The ability to achieve high cycling rates in a lithium-ion battery is limited by the Li transport within the electrolyte; the transport of Li ions and electrons within the electrodes; and, when a phase transformation is induced as a result of the Li compositional changes within an electrode, the nucleation and growth of the second phase. The absence of a phase transformation involving substantial structural rearrangements and large volume changes is generally considered to be key for achieving high rates. This assumption has been challenged by the discovery that some nanoparticulate electrode materials, most notably LiFePO4, can be cycled in a battery at very high rates, even though they cycle between two phases during battery operation. This apparent contradiction has been reconciled by the hypothesis that a nonequilibrium solid solution can be formed during reaction to bypass the nucleation step.

Embedded Image

Phase transformation from LiFePO4 (blue) to FePO4 (red). The delithiation (indicated by yellow arrows) proceeds at high rates via the formation of a nonequilibrium solid solution phase LixFePO4 (intermediate purple color), avoiding a classical nucleation process (indicated by dashed arrows). When the reaction is interrupted, the particles relax into the equilibrium configuration (shaded region), where only single-phase particles of LiFePO4 and/or FePO4 are present.

Rationale

To test this proposal, in situ techniques with high temporal resolution must be used to capture the fast phase transformation processes. We performed in situ synchrotron x-ray diffraction (XRD), which readily detects the structural changes and allows for fast data collection, on a LiFePO4-Li battery at high cycling rates, conditions that are able to drive the system away from equilibrium. We used an electrode comprising ~190-nm LiFePO4 particles, carbon, and binder (30:60:10 weight %), along with an electrochemical cell designed to yield reproducible results over multiple cycles, even at high rates. The high carbon content ensures that the reaction at high rates is not limited by either the electronic conductivity or ionic diffusion within the electrode composite. We compared the experimental results with simulated XRD patterns, in which the effects of strain versus compositional variation were explored. We then adapted a whole-pattern fitting method to quantify the compositional variation in the electrode during cycling.

Results

The XRD patterns, collected during high-rate galvanostatic cycling, show the expected disappearance of LiFePO4 Bragg reflections on charge and the simultaneous formation of FePO4 reflections. In addition, the development of positive intensities between the LiFePO4 and FePO4 reflections indicates that particles with lattice parameters that deviate from the equilibrium values of LiFePO4 and FePO4 are formed. The phenomenon is more pronounced at high currents. Detailed simulations of the XRD patterns reveal that this lattice-parameter variation cannot be explained by a LiFePO4-FePO4 interface within the particles, unless the size of the interface is similar to or greater than the size of the entire particle. Instead, the results indicate compositional variation either within or between particles.

Conclusion

The results demonstrate the formation of a nonequilibrium solid solution phase, LixFePO4(0 < x < 1), during high-rate cycling, with compositions that span the entire composition between two thermodynamic phases, LiFePO4 and FePO4. This confirms the hypothesis that phase transformations in nanoparticulate LiFePO4 proceed, at least at high rates, via a continuous change in structure rather than a distinct moving phase boundary between LiFePO4 and FePO4. The ability of LiFePO4 to transform via a nonequilibrium single-phase solid solution, which avoids major structural rearrangement across a moving interface, helps to explain its high-rate performance despite a large Li miscibility gap at room temperature. The creation of a low-energy nonequilibrium path by, for example, particle size reduction or cation doping should enable the high-rate capabilities of other phase-transforming electrode materials.

Watching battery materials in action

When batteries get rapidly charged and discharged repeatedly, they will often stop working. This is especially true when the cycling changes the crystal structure of the battery components. Liu et al. examined the structural changes in components of a type of lithium battery (see the Perspective by Owen and Hector). Their findings explain why LiFePO4 delivers unexpectedly good electrochemical performances, particularly during rapid cycling.

Science, this issue p. 10.1126/science.1252817; see also p. 1451

Abstract

The absence of a phase transformation involving substantial structural rearrangements and large volume changes is generally considered to be a key characteristic underpinning the high-rate capability of any battery electrode material. In apparent contradiction, nanoparticulate LiFePO4, a commercially important cathode material, displays exceptionally high rates, whereas its lithium-composition phase diagram indicates that it should react via a kinetically limited, two-phase nucleation and growth process. Knowledge concerning the equilibrium phases is therefore insufficient, and direct investigation of the dynamic process is required. Using time-resolved in situ x-ray powder diffraction, we reveal the existence of a continuous metastable solid solution phase during rapid lithium extraction and insertion. This nonequilibrium facile phase transformation route provides a mechanism for realizing high-rate capability of electrode materials that operate via two-phase reactions.

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