当前位置：文档库 › Phase Stability of Nickel Hydroxides and Oxyhydroxides

Phase Stability of Nickel Hydroxides and Oxyhydroxides

A.Van der Ven,a,z D.Morgan,b Y.S.Meng,c and G.Ceder c,*

a Department of Materials Science and Engineering,University of Michigan,Ann Arbor,Michigan48109,

USA

b Department of Materials Science and Engineering,University of Wisconsin,Madison,Wisconsin53706,

USA

c Department of Materials Science an

d Engineering,Massachusetts Institut

e o

f Technology,Cambridge,

Massachusetts02139,USA

We investigate phase stability of several nickel hydroxides from?rst-principles.Hydrogen removal from?-Ni?OH?2is predicted to occur through a biphasic reaction to?-NiOOH involving a change in the stacking sequence from T1?for?-Ni?OH?2?to P3?for ?-NiOOH?.Further topotactic removal of hydrogen from?-NiOOH can only occur after a step in a range between0.4and0.9V is surpassed.We also propose an energetically stable crystal structure for stoichiometric?-NiOOH,which offers an explanation for the oxidation limit of3.66for Ni.In this structure,potassium in the intercalation layer resides halfway between adjacent trigonal prismatic sites.We conclude with a discussion of the role of the electrolyte in determining phase stability as well as the voltage pro?le of?-NiOOH.

Manuscript submitted March4,2005;revised manuscript received September12,2005.

Available electronically December14,2005.

Nickel hydroxide compounds are widely used as cathodes in pri-

mary and secondary alkaline batteries.Several different forms of

nickel hydroxide exist,each differing in crystal structure and com-

position.Important nickel hydroxide variants are referred to as ?-NiOOH,?-Ni?OH?2,?-NiOOH,and?-Ni?OH?2.During charge and discharge,a variety of phase transformations can occur between

the different nickel hydroxide variants.The Bode diagram?Fig.1?1

qualitatively captures most of the essential phase transformations in Ni hydroxide electrodes.Charging of??II?nickel hydroxide Ni?OH?2leads to??II?nickel oxyhydroxide NiOOH.Ni in ??II?–Ni?OH?2has a valence of+2while Ni in??III?–NiOOH has a valence of+3.The??III?–NiOOH compound can either be dis-charged back to Ni?OH?2,or it can be charged even further,trans-forming to?-NiOOH,a phase that is poorly characterized but is nevertheless known to contain water molecules and potassium which are drawn from the alkaline electrolyte.2Upon discharge,the ?phase transforms under most conditions to an?-Ni?OH?2which, like?,also contains water molecules along with other molecules from the electrolyte or air,such as CO32?or NH2?.2Electrochemical cycling can occur over the?→?transformation,but?usually transforms to??II?after some time.?-NiOOH has also been ob-served to transform directly to??II?–Ni?OH?2upon discharge,by-passing the?phase.3

Although the general features of Ni-hydroxide-based electrode materials have been characterized over the last century,1,2,4many of their basic properties remain unknown.Important questions persist about the precise crystal structures of?-NiOOH and?-NiOOH. Furthermore,the relationship between the crystal structures of?and ?-NiOOH and their measured capacities are still unclear.While it has not been possible to extract more than one electron per Ni ion in the?-Ni?OH?2to?-NiOOH couple,more than one electron per Ni can be cycled if the?phase participates in the couple.Oxidation of the?phase has,however,been limited to a maximum oxidation state for Ni of+3.66,5,6although the reason for this limitation is not understood.Further oxidation of?by either chemical or electro-chemical means might produce an electrode capable of cycling two electrons per Ni,thereby signi?cantly enhancing the capacity of alkaline cells.Cycling of Ni2+to Ni4+has been demonstrated in Li-ion batteries.7

In this paper,we investigate the phase stability of nickel hydrox-ides from?rst-principles.We predict that the previously uncharac-terized crystal structure of??III?–NiOOH is actually derived from the P3host.Furthermore,we identify a plausible crystal structure for the?-NiO2?H2O?0.67K0.33H x phase that is consistent with avail-able experimental observations.The proposed crystal structure has a

P3host and the K ions reside exactly between adjacent trigonal

prismatic sites of the intercalation layer.We have also calculated the topotactic voltage curves for the?and?phases,and predict the existence of a large step in voltage at?-NiOOH,which effectively limits the capacity of the?Ni-hydroxide compound to one electron per Ni ion.

Methodology

We combine?rst-principles electronic structure calculations with

a cluster expansion approach for the disorder of protons in the ma-

terials to calculate phase stability and thermodynamic properties of

the nickel hydroxide system.The electronic structure calculations

yield information about solids at zero Kelvin,including energy dif-

ferences between different crystal structures,equilibrium lattice pa-

rameters,and electronic charge densities.For solids exhibiting con-

?gurational disorder?e.g.,resulting from the many possible

arrangements of hydrogen atoms and vacancies within the hydroxide

host structures at nonstoichiometric compositions?,the energies cal-

culated with electronic structure methods can be combined with a

lattice model formalism?i.e.,the cluster expansion?and Monte

Carlo simulations to obtain?nite temperature thermodynamic prop-

erties such as phase diagrams and voltage curves.This approach has

been successfully applied to study phase stability in a wide variety

of oxides,and we refer the reader to the following references for

more details.8-11

The energies calculated with electronic structure methods were

performed in the generalized gradient approximation?GGA?to den-

sity functional theory using the pseudopotential method.While this

is one of the most accurate?rst-principles approaches,documented

problems on transition metal oxides exist.12,9Nevertheless,based on our previous work on Li x CoO2and Li x NiO2,8-10we do not believe these would affect the outcome of our?ndings,which focus on determining relative stabilities and qualitative variations in voltage pro?les with hydrogen concentration.The particular numerical implementation used for this work was a plane-wave projector aug-mented wave?PAW?13,14pseudopotential method as coded in the Vienna Ab-initio Simulation Package?V ASP?.15All calculations were spin polarized initialized with ferromagnetic magnetization.

Phase Stability of?-H x NiO2

The transformation from??II?–Ni?OH?2to??III?–NiOOH upon charging of the nickel hydroxide compound is well known to be a

*Electrochemical Society Active Member. z E-mail:avdv@https://www.wendangku.net/doc/0b15581069.html, Journal of The Electrochemical Society,153?2?A210-A215?2006?0013-4651/2005/153?2?/A210/6/$15.00?The Electrochemical Society

A210

biphasic reaction.16While the crystal structure of ??II ?–Ni ?OH ?2is isomorphic with CdI 2?which has the T1stacking sequence ?,that of ??III ?–NiOOH has not been characterized.2,3The crystal structure of ?-Ni ?OH ?2consists of close-packed oxygen planes with an ABAB stacking sequence.2The Ni atoms occupy octahedral sites between alternating oxygen layers,and the hydrogen atoms reside in the tetrahedral sites of the remaining layers between oxygen.The hydrogen atoms do not reside at the centers of the tetrahedral sites but are tightly bound to one of the four oxygen atoms surrounding the tetrahedral sites as illustrated in Fig.2.For convenience,we will also write ?-Ni ?OH ?2as ?-H 2NiO 2,which upon removal of hydro-gen during charging becomes ?-H x NiO 2with x ranging between 0and 2.Written in this form,it becomes clear that ?nickel hydroxide consists of a rigid NiO 2host ?which can undergo structural transfor-mations ?and removable H atoms that occupy interstitial sites within the host.

The phases that are thermodynamically stable and appear in equilibrium for the H x NiO 2system as a function of hydrogen con-centration are those with the lowest Gibbs free energy.Free energies of oxide compounds such as the ?-Ni-hydroxides can be calculated by combining ?rst-principles electronic structure methods with tools from statistical mechanics ?cluster expansion combined with Monte Carlo simulations ?.8-10To this end,we calculated the energy of a variety of different hydrogen-vacancy arrangements ?eight con?gu-rations ?over the tetrahedral sites of the T1host structure of NiO 2for hydrogen concentrations ranging from x =0to 2within GGA using the PAW pseudopotential method.We also calculated the energy of different hydrogen arrangements within the P3host structure of NiO 2?six con?gurations ?.This host structure consists of an AAB-BCC oxygen stacking sequence,which can be derived from the T1ABAB stacking sequence by gliding the O–Ni–O slabs of T1with respect to each other to yield an AA stacking sequence across the intercalation layer ?where hydrogen resides ?.As in T1-NiO 2,the Ni ions in the P3structure reside in octahedral sites between oxygen planes with an AB stacking sequence.We considered the P3host structure in addition to that of T1for two reasons:?i ?it is observed to be the crystal structure of ?-CoOOH;17?ii ?the AA oxygen stack-ing sequence across the intercalation layers allows hydrogen atoms to form strong primary and secondary hydrogen bonds with oxygen atoms as illustrated in Fig.2.

The calculated energies for different arrangements in T1and P3H x NiO 2were used to parameterize the interaction parameters of

lattice models ?i.e.,cluster expansions ?,one for each host structure ??ve interaction parameters for the cluster expansion of the T1host,and six interaction parameters for the cluster expansion of the P3host ?,which were then combined with Monte Carlo simulations to calculate ?nite temperature Gibbs free energy curves.Figure 3illus-trates calculated free energies of ?-H x NiO 2at room temperature.As is clear from Fig.3,the T1crystal structure is not the most favored thermodynamically,as hydrogen is extracted from ?-Ni ?OH ?2.In-stead,the free energy of the solid is lowered if it phase

separates

Figure 1.The Bode diagram illustrating the different variants of Ni-hydroxide and the possible phase transformations between

them.

Figure 2.The crystal structures of ?-Ni ?OH ?2having the T1oxygen stack-ing sequence ?ABAB ?and ?-NiOOH having the P3oxygen stacking se-quence ?AABBCC ?.Also shown ?right ?is local coordination of hydrogen ?small circles ?by oxygen ?large circles ?

Figure 3.Calculated Gibbs free energies for the T1and P3forms of H x NiO 2.The dashed line corresponds to the common between the T1and P3free energy curves and signi?es a two-phase coexistence region between Ni ?OH ?2and NiOOH.

A211

Journal of The Electrochemical Society ,153?2?A210-A215?2006?

into a two-phase mixture of T1having stoichiometry Ni?OH?2and a phase with crystal structure P3having stoichiometry NiOOH.The free energy of this two-phase mixture is given by the common tan-gent?dashed line in Fig.3?to the free energies of T1at x=2and P3 at x=1.Hence,the?rst-principles calculations predict that P3 NiOOH forms through a biphasic reaction from T1upon charge.

While not evident from the free energy curves in Fig.3,our ?rst-principles calculations not only indicate that P3HNiO2is more stable than T1HNiO2,but that T1HNiO2is actually dynamically unstable,and spontaneously transforms to P3without encountering an energy barrier.We found that several of the ordered hydrogen-vacancy arrangements we considered at x=1make the T1host structure of NiO2dynamically unstable,inducing a spontaneous change in the stacking sequence of the oxygen layers from an ABAB sequence to the AABBCC sequence of P3.

The relative stability between T1and P3HNiO2?i.e.,NiOOH?can be directly attributed to the local environment of the hydrogen atoms within the intercalation layers.While T1and P3have identi-cal O–Ni–O slabs,crucial differences exist between their stacking sequences across the H intercalation layer.In the P3crystal struc-ture,the oxygen atoms directly face each other across the intercala-tion plane as illustrated in Fig.2.This makes it possible for the hydrogen atoms to tightly bind to one of the oxygen atoms of one O–Ni–O slab?covalent bond with a calculated length of?1.1??and to form an energetically favorable hydrogen bond with the oxy-gen atom of the adjacent O–Ni–O slab?with a calculated bond length of?1.4??.The ability to form a secondary hydrogen bond

is absent in the T1crystal structure,making it energetically unfavor-able compared to P3once hydrogen is removed from Ni?OH?2. Within the tetrahedral sites of T1,the H forms a covalent bond with one oxygen atom?with calculated bond length of?1??but is too far??2.3??from its three other nearest-neighbor oxygen atoms to form any favorable secondary hydrogen bonds.The T1structure only forms at x=2in H x NiO2,because the P3structure does not have enough H sites to accommodate the two hydrogen atoms per formula unit.

Because the Gibbs free energy contains all relevant thermody-namic properties of a system at constant pressure and temperature, other thermodynamic properties such as the intercalation voltage can also be obtained in a straightforward manner.In fact,the voltage is linearly related to the chemical potential of hydrogen within H x NiO2 and the chemical potential is proportional to the slope of the free energy curves illustrated in Fig.3.Figure4illustrates the predicted voltage pro?le of H x NiO2as the hydrogen content is varied.While the relative variation of the voltage is well predicted from?rst-principles,there is currently no accurate methodology to calculate reference states for hydrogen.Hence,the absolute value of the volt-age cannot be predicted from?rst-principles.To facilitate compari-son with experiment,we shifted all calculated voltages by a constant such that the predicted voltage of the NiOOH→Ni?OH?2couple is set to zero.Then for any speci?c anode,the voltage curve of Fig.4 can be shifted uniformly by an amount that is equal to the equilib-rium open-cell voltage measured during the??III?→??II?couple. The plateau between x=1and2corresponds to the voltage of the biphasic reaction as T1Ni?OH?2transforms to P3NiOOH upon charge,or the reverse reaction upon discharge.?There is no polar-ization between calculated charge and discharge voltages because the solid lines represent the open-circuit voltage at complete equi-librium.?

The predicted voltage pro?le for the?structure exhibits a large step at x=1close to0.9V.This step arises from the energetic stability of the P3crystal structure of?-NiOOH in which the hy-drogen atoms can form energetically favorable O–H–O bonds as illustrated in Fig.2.Further removal of hydrogen from P3NiOOH would require breaking these energetically favorable bonds.A siz-able increase in voltage is therefore necessary to remove hydrogen from P3?-NiOOH.We note that predicted voltages are often modi-?ed when treating electron correlation in the DFT+U method.12,18Using GGA+U with U values between3and6eV predicts a step

of around0.4V at x=1as compared to0.9V calculated with GGA.We expect the actual voltage step to be somewhere between these two values.A voltage step between0.4and0.9eV,needed to oxidize Ni beyond+3in this structure,makes it unlikely that sub-

stantially more capacity will be obtained from the?phase with aqueous electrolytes.It is,however,possible that further charging at

lower potential is possible by conversion of the?phase to another

phase?such as??.

The?-NiOOH Phase

The?-NiOOH phase represents a family of Ni-hydroxide com-pounds characterized by a large interlayer sheet distance.2The gen-

eral chemical formula of the?form can be written as

H x A y?H2O?z NiO2in which A is typically Na or K and y and z are often claimed to be0.33and0.66,respectively.2,19A common

form2,5of?is H x K0.33?H2O?0.66NiO2,which can be obtained by overcharging?-NiOOH.The potassium and water come from the electrolyte according to a reaction such as

3???NiOOH?+KOH+H2O→H2K?H2O?2Ni3O6

The crystal structure of?-H x K0.33?H2O?0.66NiO2is poorly charac-terized,though it is known that?has a P3oxygen stacking sequence2similar to that predicted in this work for?-NiOOH.Fur-thermore,experimental evidence suggests that the maximal oxida-tion state of Ni in the?phase is+3.66.2,5,6

Starting with the stoichiometric chemical formula for??namely, H x K0.33?H2O?0.66NiO2?,we used?rst-principles total energy calcu-lations to determine an energetically stable crystal structure for this phase.An energetically stable form of H x K0.33?H2O?0.66NiO2is il-lustrated in Fig.5,which shows both a projection?along the direc-tion perpendicular to the close-packed oxygen planes?and a side view of the intercalation layer of the crystal structure.The structure has an AABBCC oxygen stacking sequence as in P3,which is con-sistent with what has been observed experimentally.The K atoms, which are ordered in a?3a??3a superlattice,do not reside at the center of a prismatically coordinated?by oxygen?interstitial site but instead reside at the center of a rectangle of oxygen atoms,two belonging to the O–Ni–O slab above and two belonging to the O–Ni–O slab below.In this way,K atoms avoid sites that share faces with Ni either from above or below the intercalation layer.

The Figure 4.Calculated equilibrium voltage curve for?nickel hydroxide within the GGA approximation?the GGA+U approximation predicts a smaller voltage step of close0.4V?.The reference state for the anode has been arbitrarily chosen such that the plateau corresponding to the ??II????III?couple is zero.To compare to experiment,the whole curve should be shifted by an amount equal to the measured voltage for the ??II????III?couple.

A212Journal of The Electrochemical Society,153?2?A210-A215?2006?

water molecules are oriented such that the vector connecting the two H atoms of each water molecule is perpendicular to the O–Ni–O slabs.

It is likely that the K and water molecules behave as inert com-ponents during topotactic ?i.e.,without changing the structure ?charging and discharging of the ?-phase.In that case,the other hydrogen atoms which are bound to oxygen atoms of the O–Ni–O slabs can be removed from the ?crystal structure.These hydrogen atoms are indicated by arrows in Fig.5.There are four active hy-drogen sites for every three Ni atoms.This means that x in the stoichiometric formula for ?-H x K 0.33?H 2O ?0.66NiO 2can only range from 0to 1.33.When x =0,the valence of Ni is +3.66.When x =1.33,the valence of Ni is +2.33.When half the active hydrogen sites are ?lled,the valence of Ni is exactly +3.In this proposed ?crystal structure,it is clearly crystallographic factors that impose the seemingly arti?cial bound of +3.66on the maximum oxidation state of the Ni atoms.This suggests that higher Ni valence states,and associated larger cathode capacities,might be realized through struc-tural modi?cation.

The proposed crystal structure for ?illustrated in Fig.5has a monoclinic unit cell and belongs to the C 2/m space group.Table I lists calculated lattice parameters ?calculated at x =0.66in H x K 0.33?H 2O ?0.66NiO 2?along with the calculated coordinates of the asymmetric unit cell for the atoms of the crystal ?taken from calcu-lations at x =1.33in H x K 0.33?H 2O ?0.66NiO 2where all hydrogen

sites are ?lled ?.We emphasize that we have only demonstrated that this structure for ?-NiOOH is locally stable ?i.e.,it is mechanically stable against deformation into another structure ?.The arrangement of hydrogen,potassium,and water molecules between the O–Ni–O slabs may only correspond to a local minimum in energy and not a global minimum.Nevertheless,while we have not exhausted all possible hydrogen,potassium,and water arrangements within the intercalation layer,the proposed crystal structure is consistent with what is currently known about the ?-phase.The monoclinic symme-try of the structure of Fig.5and Table I results from the superlattice ordering of the K and water molecules in the intercalation layer.In real crystals,however,it is likely that the K and water molecules of ?-NiOOH are not perfectly ordered but instead exhibit short-range order that is similar to that in Fig.5on a local level.In that case,the symmetry of the crystal adopts that of the host structure,which for the P3stacking is R 3ˉm symmetry.An important feature of this crys-tal structure is that the K atoms do not reside in a trigonal prismatic site of the intercalation layer of the P3host but rather reside exactly between adjacent trigonal prismatic sites.

Because the formation of ?upon overcharging or oxidizing of ?-NiOOH is accompanied by the uptake of K and H 2O,and because discharging of ?proceeds through a transformation to ?or ?-Ni ?OH ?2,it is experimentally dif?cult ?if not impossible ?to iso-late the topotactic voltage pro?le for the ?phase.With ?rst-principles computational tools,calculating a topotactic voltage pro-?le is straightforward.Figure 6illustrates the topotactic voltage pro?le for the proposed structure of stoichiometric ?-H x K 0.33?H 2O ?0.66NiO 2as the hydrogen content is varied from x =0to 1.33.The voltage curve was calculated with Monte Carlo simulations applied to a lattice model Hamiltonian ?six interaction terms ?that was ?t to GGA ?rst-principles energies of seven hydrogen-vacancy arrangements in the ?-K 0.33?H 2O ?0.66NiO 2host.The same reference state for the anode was used as for the ?couple.Two plateaus are predicted,separated by a step of almost 1V at x =0.66?corresponding to a Ni valence state of +3?.The step in the voltage pro?le is not observed experimentally,as ?never discharges topotactically but rather transforms to either ?or ?.The voltage plateau between x =0and 0.66could potentially be observed when ?is charged beyond a Ni oxidation state of +3.

In our calculations several approximations were made.These in-clude the neglect of hydrogen vibrational degrees of freedom and the vibrational zero point energies.While vibrational degrees

Figure 5.Intercalation layer of proposed crystal structure for ?-NiOOH.The proposed structure for ?-NiOOH has a P3oxygen stacking sequence with Ni residing in octahedral sites.

Table I.Calculated lattice parameters and asymmetric unit cell for the proposed ?crystal structure.The proposed structure has a monoclinic unit cell (doubly primitive,face centered)and be-longs to the C 2/m space group.The ?rst set of H sites has partial occupancy as x is varied in H x K 0.33…H 2O …0.66NiO 2.

a =5.1

b =9.1

c =6.84?=90.0?=105.7?=90.0

H 8j ?x =0.4042y =0.0802z =0.3435?H 8j ?x =0.4620y =0.2643z =0.3651?

K 2d ?001/2?Ni 2a ?000?4g ?0y =0.28910?O 4h ?0y =0.29391/2?4i ?x =0.37390z =0.2491?8j ?x =0.3718y =0.6564z =0.1480

Figure 6.Calculated topotactic voltage curve of ?-NiOOH within the GGA approximation.The reference state for the anode is the same as that used in Fig.4.

A213

Journal of The Electrochemical Society ,153?2?A210-A215?2006?

freedom can safely be ignored for most elements,they are important for hydrogen.Because of this,the voltages predicted for the two voltage plateaus are only approximate and quantitative comparisons with experiment must be avoided.Furthermore,the topotactic volt-age pro?le of Fig.6is for a stoichiometric?phase with exactly 0.33K and0.66H2O molecules in the intercalation layers.In the experiment,the potassium and water contents may deviate from these stoichiometric values which will also change the voltage.

Discussion

Our?rst-principles study of phase stability in the H x NiO2system predicts that?-NiOOH has a different oxygen stacking sequence than?-Ni?OH?2.?-NiOOH is stable in the P3structure with an

AABBCC oxygen stacking sequence,while?-Ni?OH?2is stable in the T1host with ABAB stacking sequence.This has important im-plications for the??II?→??III?transformation,as it requires a re-shuf?ing of the oxygen planes across the intercalation layers.One mechanism by which such structural phase transformations can oc-cur is by passage of dislocations through the intercalation layers.20 The work by Delmas et al.19suggests,however,that this may not be the dominant mechanism to kinetically facilitate the??II?→??III?transformation.They showed that oxidation of Ni?OH?2 leads to a NiOOH compound having an amorphous-like X-ray dif-fraction pattern?XRD?,which nevertheless,reverts back to a crys-talline form of Ni?OH?2upon reduction.While passage of disloca-

tions to facilitate the??II?→??III?transformation will introduce structural defects which could conceivably lead to an amorphization of the host structure,the damage resulting from dislocation passage is irreversible and is unlikely to be removed upon reduction of NiOOH to Ni?OH?2.Instead,the mechanism by which the??II?→??III?transformation actually proceeds may be linked to the oc-currence of noncooperative Jahn-Teller distortions of the oxygen octahedra around the Ni ions,observed by Delmas et al.19in NiOOH.Such noncooperative Jahn-Teller distortions in NiOOH can locally accommodate the strain induced by the stacking sequence change during the??II?→??III?transformation,and because the strain accommodation is local,the stacking sequence shifts need not be cooperative over long distance,leading to a structure that may appear amorphous with XRD measurements.We note that in our GGA pseudopotential calculations,we were unable to stabilize a cooperative Jahn-Teller distortion in the P3form of NiOOH.

An important prediction in this work is the large voltage step at x=1in H x NiO2.This step,which arises from the strong hydrogen bonds with oxygen in the P3NiOOH crystal structure?Fig.2?,es-sentially limits the capacity of?Ni-hydroxide compounds to one electron per Ni in conventional aqueous electrolytes.A step in the voltage pro?le between0.4and0.9V is unlikely to be eliminated by

chemical substitution.In aqueous electrolytes,further charge of ?-NiOOH leads to a transformation to the?phase which forms upon uptake of potassium and water.2Only with nonaqueous elec-trolytes is it conceivable that the full topotactic H x NiO2voltage curve?with x ranging between0and2?can be realized in an elec-trochemical cell.

With a detailed crystallographic model for ?-H x K0.33?H2O?0.66NiO2,it is possible to calculate a topotactic volt-age curve.Our calculations suggest that the topotactic voltage curve for this crystal structure consists of two plateaus separated by a step approaching1V at a hydrogen concentration corresponding to a Ni valence state of+3.In experiment,it is unlikely that a topotactic voltage curve for?-NiOOH can be isolated,as the formation of?and its subsequent two-phase equilibria with either a?or?nickel hydroxide involves the insertion or removal not only of hydrogen but also potassium and water molecules from the electrolyte.

It is the ability of both the?and?nickel hydroxides to exchange atoms and molecules with the electrolyte that sets these phases apart from most other intercalation compounds.The fact that these phases can exchange components with the electrolyte during charge and discharge means that their voltage depends not only on the state of charge,but also on the thermodynamic state of the electrolyte.For intercalation compounds such as?-H x NiO2,which do not exchange species with the electrolyte,the equilibrium voltage of the com-pound at?xed temperature?and for a?xed anode?is a function only of the overall hydrogen concentration in the compound.Indeed,the voltage is linearly related to the chemical potential of hydrogen within the compound,which is equal to the slope of the Gibbs free energy of the host with respect to x,as illustrated schematically in Fig.7a.This slope is independent of the composition of the electro-lyte.

Compounds that are able to exchange matter with the electrolyte tend to equilibrate with the electrolyte.The hydrogen chemical po-tential and hence the voltage for such compounds is affected by the equilibrium reached between the cathode and the electrolyte.While a compound such as?-NiOOH can exchange several species with the electrolyte,the basic principles can be illustrated with a simple hypothetical compound that only exchanges one component with the electrolyte.Figure7b illustrates a Gibbs free energy plot for a host structure M that can intercalate hydrogen,H;and simultaneously absorb species A from the electrolyte.The chemical potentials?A,?H,and?M for the different species at a given mole fraction x A

and Figure7.Schematic Gibbs free energies for topotactic intercalation?a?and intercalation accompanied by mass exchange with the electrolyte?b?.M corresponds to the host,H to hydrogen,and A to a species of the electrolyte that can be incorporated within the host during charge and discharge.

A214Journal of The Electrochemical Society,153?2?A210-A215?2006?

x H are determined by the intercept of the plane tangent to the Gibbs free energy curve at x A and x H with the axes x A=1,x H=1,and x M=1,respectively.

The chemical potential of A in the electrolyte is determined by the overall composition of the electrolyte.An increase in the com-position of A in the electrolyte,holding all other species constant, leads to an increase in the chemical potential of A.?It is customary to speak of the activity of a component of the electrolyte instead of its chemical potential,the former being proportional to the exponen-tial of the latter.?If the intercalation compound is in equilibrium with the electrolyte?with respect to exchange of A?,then the com-position of A in the intercalation compound at?xed state of charge ?i.e.,H composition?must be such that the plane tangent to the Gibbs free energy of the host intersects the x A=1axis at ?A=?A electrolyte.Hence,the chemical potential of A in the electrolyte

and the state of charge determine the equilibrium concentration of A in the intercalation compound.Figure7b also illustrates that in gen-eral,as the state of charge?i.e.,hydrogen concentration?varies,the equilibrium concentration of A in the compound will change as well. Furthermore,and more importantly,a change in the chemical poten-tial of A in the electrolyte will result in a different voltage pro?le,as the hydrogen chemical potential of the compound depends on ?A=?A electrolyte.This illustrates that the voltage of compounds such as?and?nickel hydroxide can be tailored not only by chemical modi?cation of the compound itself?through chemical substitution of the compound,for example?,but also by modifying the electro-lyte.For?and?nickel hydroxide,the equilibrium with the elec-trolyte is more complicated than schematically illustrated in Fig.7b, as several species can be exchanged with the electrolyte,thereby precluding any graphical representation of such equilibrium.How-ever,the principles are the same as those illustrated in Fig.7b,and the more complex equilibrium problem could be studied with gen-eral electrolyte solution theory.

Conclusion

We have investigated phase stability among several variants of Ni-hydroxide from?rst-principles.Our calculations within the GGA predict that?-Ni?OH?2,stable in the T1crystal structure,transforms upon charging through a biphasic reaction to?-NiOOH having a P3 crystal structure.Hence,the calculations predict that in thermody-namic equilibrium,?-NiOOH has a host structure with a different oxygen-stacking sequence from that of?-Ni?OH?2,which points attention to the importance of defects in the material to facilitate the transformation and reduce hysteresis between charge and discharge. The calculations also predict that further hydrogen removal from ?-NiOOH is unlikely with aqueous electrolytes and with retention

of the structure.We have also proposed an energetically stable crys-tal structure for?-NiOOH which is consistent with available experi-mental evidence,and which offers a crystallographic explanation for the oxidation limit of3.66for Ni in these compounds.

Acknowledgments

We are grateful for?nancial support from Duracell.We also thank George Cintra,Paul Christian,and Francis Wang from Dura-cell for helpful discussions.

The University of Michigan assisted in meeting the publication costs of this article.

References

1.H.Bode,K.Dehmelt,and J.Witte,Electrochim.Acta,11,1079?1966?.

2.P.Oliva,J.Leonardi,https://www.wendangku.net/doc/0b15581069.html,urent,C.Delmas,J.J.Braconnier,M.Figlanz,F.

Fievet,and A.De Guibert J.Power Sources,8,229?1982?.

3. F.Barde,M.R.Palacin,Y.Chabre,O.Isnard,and J.M.Tarascon,Chem.Mater.,

16,3936?2004?.

4. F.Barde,M.R.Palacin,B.Beaudoin,and J.M.Tarascon,Chem.Mater.,17,470

?2005?.

5. D.A.Corrigan and S.L.Knight,J.Electrochem.Soc.,136,613?1989?.

6.J.DeSilvestro,D.A.Corrigan,and M.J.Weaver,J.Electrochem.Soc.,135,885

?1988?.

7.J.Reed and G.Ceder,Electrochem.Solid-State Lett.,5,A145?2002?.

8. A.Van der Ven,M.K.Aydinol,G.Ceder,G.Kresse,and J.Hafner,Phys.Rev.B,

58,2975?1998?.

9.M.E.A.Y.de Dompablo,A.Van der Ven,and G.Ceder,Phys.Rev.B,66,064112

?2002?.

10. D.Carlier,A.Van der Ven,C.Delmas,and G.Ceder,Chem.Mater.,15,2651

?2003?.

11.G.Ceder,A.Van der Ven,C.Marianetti,and D.Morgan,Modell.Simul.Mater.Sci.

Eng.,8,311?2000?.

12. F.Zhou,M.Cococcioni,C.A.Marianetti,D.Morgan,and G.Ceder,Phys.Rev.B,

70,235121?2004?.

13.P.E.Blochl,Phys.Rev.B,50,17953?1994?.

14.G.Kresse and D.Joubert,Phys.Rev.B,59,1758?1999?.

15.G.Kresse and J.Furthmuller,Comput.Mater.Sci.,6,15?1996?.

16. C.Leger,C.Tessier,M.Menetrier,C.Denage,and C.Delmas,J.Electrochem.

Soc.,146,924?1999?.

17.M.Butel,L.Gautier,and C.Delmas,Solid State Ionics,122,271?1999?.

18.M.Cococcioni and S.de Gironcoli,Phys.Rev.B,71,035105?2005?.

19. A.Demourgues,L.Gautier,A.V.Chadwick,and C.Delmas,,Nucl.Instrum.

Methods Phys.Res.B,133,39?1997?.

20.H.Gabrisch,R.Yazami,and B.Fultz,Electrochem.Solid-State Lett.,5,A111

?2002?.

A215

Journal of The Electrochemical Society,153?2?A210-A215?2006?