A lithium superionic conductor
Noriaki Kamaya 1,Kenji Homma 1,Yuichiro Yamakawa 1,Masaaki Hirayama 1,Ryoji Kanno 1*,Masao Yonemura 2,Takashi Kamiyama 2,Yuki Kato 3,Shigenori Hama 3,Koji Kawamoto 3and Akio Mitsui 4
Batteries are a key technology in modern society 1,2.They are ud to power electric and hybrid electric vehicles and to store wind and solar energy in smart grids.Electrochemical devices with high energy and power densities can currently be powered only by batteries with organic liquid electrolytes.However,such batteries require relatively stringent safety precautions,making large-scale systems very complicated and expensive.The application of solid electrolytes is currently limited becau they attain practically uful conductivities (10−2S cm −1)only at 50–80◦C,which is one order of magni-tude lower than tho of organic liquid electrolytes 3–8.Here,we report a lithium superionic conductor,Li 10GeP 2S 12that has a new three-dimensional framework structure.It exhibits an extremely high lithium ionic conductivity of 12mS cm −1at room temperature.This reprents the highest conductivity achieved in a solid electrolyte,exceeding even tho of liquid org
anic electrolytes.This new solid-state battery electrolyte has many advantages in terms of device fabrication (facile shaping,patterning and integration),stability (non-volatile),safety (non-explosive)and excellent electrochemical proper-ties (high conductivity and wide potential window)9–11.
The great demand for batteries with high power and energy densities promotes the need for advanced lithium-ion and lithium–air battery technologies 1,2.Solid electrolytes promi the potential to replace organic liquid electrolytes and thereby improve the safety of next-generation high-energy batteries.Although the advantages of non-flammable solid electrolytes are widely acknowledged,their low ionic conductivities and low chemical and electrochemical stabilities prevent them being ud in practical applications.
In an effort to overcome the problems,there has been an ongoing arch over the past few decades for new materials for solid electrolytes.This arch has considered crystalline,glassy,polymer and composite systems.Despite the efforts,lithium nitride (Li 3N),which was discovered in the 1970s (ref.12),still has the highest ionic conductivity (6×10−3S cm −1at room temperature)of potential solid electrolytes 13.Unfortunately,its low electrochemical decomposition potential prevents it being ud in practical applications.Other systems currently being investigated a
s battery electrolytes are crystalline materials (such as oxide perovskite,La 0.5Li 0.5TiO 3(ref.3)and thio-LISICON,Li 3.25Ge 0.25P 0.75S 4(ref.4)),glass ceramics (Li 7P 3S 11;refs 5,6)and glassy materials (Li 2S–SiS 2–Li 3PO 4;refs 7,8);all the materials exhibit ionic conductivities of the order of 10−3S cm −1,which is lower than that of lithium nitride.Polymer electrolytes are commonly complexes of a lithium salt and high-molecular-weight
灶神之妻1Department of Electronic Chemistry,Interdisciplinary Graduate School of Science and Engineering,T okyo Institute of T echnology,4259Nagatsuta,Midori,
Yokohama 226-8502,Japan,2Neutron Science Laboratory (KENS),Institute of Materials Structure Science,High Energy Accelerator Rearch
Organization (KEK),1-1Oho,Tsukuba,Ibaraki 305-0801,Japan,3T oyota Motor Corporation,Battery Rearch Division,Higashifuji T echnical Center,1200Mishuku,Susono,Shizuoka 410-1193,Japan,4T oyota Motor Corporation,Material Engineering Management Division,Material Analysis Department,1T oyota-cho,T oyota,Aichi 471-8572,Japan.*e-mail:kanno@echem.titech.ac.jp.
polymers,such as polyethylene oxide,and they have very low conductivities at room temperature (∼10−5S cm −1;refs 14,15).None of the materials have conductivities comparable to tho of orga
nic liquid electrolytes and currently ud lithium-ion systems (generally of the order of 10−2S cm −1at room temperature 16).
Lithium superionic conductors,which can be ud as solid electrolytes,exhibit a high ionic diffusion in the mobile ion sublattice at temperatures well below their melting points.It is very important to understand the mechanism for fast ionic transport in solids (although it is still a relatively unusual phenomenon).It is also a challenging problem to synthesize new lithium superionic conductors.The new Li 10GeP 2S 12with a one-dimensional conduction pathway exhibits an extremely high bulk conductivity of over 10−2S cm −1at room temperature (27◦C).An all-solid-state battery with the structure LiCoO 2/Li 10GeP 2S 12/In exhibits an excellent battery performance.
Li 10GeP 2S 12was synthesized by reacting stoichiometric quan-tities of Li 2S,GeS 2and P 2S 5at 550◦C in an evacuated quartz tube.The X-ray diffraction (XRD)pattern of the reaction product indicates a new pha with structure that differs from tho of previously reported superionic conductors such as thio-LISICON (ref.4)and Li 7PS 6(ref.5).The P/Ge ratio was determined by inductively coupled plasma (ICP)spectroscopy and found to be 0.662:0.338;this value is consistent with the stoichiometric ratio of P /Ge =2.
The composition and structure of Li 10GeP 2S 12was determined by synchrotron XRD and neutron diffraction measurements.Peak indexing of the synchrotron XRD pattern revealed that the new pha has a tetragonal unit cell with cell parameters of a =8.71771(5)Åand c =12.63452(10)Åand with the extinction rule hk 0:h +k =2n ,hhl :l =2n ,00l :l =2n and h 00:h =2n ,which is characteristic of the space group P 42/nmc (137).An ab initio structure analysis determined the arrangement of PS 4and GeS 4tetrahedra in the unit cell.Synchrotron X-ray Rietveld refinements obtained using the structural model determined by the ab initio method revealed low agreement factors.On the basis of the structural model obtained by synchrotron XRD data analysis,the positions of lithium ions and the lithium content were determined by neutron Rietveld analysis.Profile fitting using the neutron diffraction data also provided low agreement factors.Supplementary Fig.S1shows a neutron Rietveld refinement pattern.Supplementary Table S1summarizes the R factors,lattice parameters and final structure parameters determined by the refinement process.The unit cell has two tetrahedral sites:4d and
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¬1
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Voltage (V) (versus Li/Li +)
a
b
Figure 1|Lithium-ion conductivity of Li 10GeP 2S 12.a ,Impedance plots of the conductivity data from low to high temperatures and Arrhenius conductivity plots of Li 10GeP 2S 12.The plotted conductivity
reprents the
sum
of
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the
grain
boundary
and bulk
conductivities.Li 10GeP 2
S 12
exhibits an extremely high ionic
conductivity even at room temperature.b
,Current–voltage curve of Li /Li 10GeP 2S 12/Au cell.The decomposition potential of the new Li 10GeP 2S 12pha exceeds 5
V.
(Ge/P)S 4
(Ge/P)S 4
LiS 61D chain (Ge/P)S 4
PS 4
LiS 6
LiS 4
LiS 4
Li (16h )Li (4d )Ge/P (4d )
P (2b )
Li (8f )
LiS 6
Li
S
a b
c
PS 4
PS 4
Figure 2|Crystal structure of Li 10GeP 2S 12.a ,The framework structure and lithium ions that participate in ionic conduction.b ,Framework structure of Li 10GeP 2S 12.One-dimensional (1D)chains formed by LiS 6octahedra and (Ge 0.5P 0.5)S 4tetrahedra,which are connected by a common edge.The chains are connected by a common corner with PS 4tetrahedra.c ,Conduction pathways of lithium ions.Zigzag conduction pathways along the c axis are
indicated.Lithium ions in the LiS 4tetrahedra (16h site)and LiS 4tetrahedra (8f site)participate in ionic conduction.Thermal ellipsoids are drawn with a 30%probability.The anisotropic character of the thermal vibration of lithium ions in three tetrahedral sites gives ri to 1D conduction pathways.
2b sites.The 4d tetrahedral site is occupied by Ge and P ions with occupancy parameters of 0.515(5)and 0.485(5),respectively.The 2b tetrahedral site is occupied only by P with an occupancy parameter of 1.00(15).The Ge /P ratio is then 4.06:1.94,which is very clo to the stoichiometric ratio of 2:1and is consistent with the composition determined by ICP analysis.There are three
lithium sites in the unit cell:16h ,4d and 8f sites,with occupancy parameters of 0.691(5),1.000(8)and 0.643(5),respectively.The number of lithium atoms in the unit cell is then calculated to be 20.200.On the basis of the ICP and neutron diffraction analys,the composition of the new pha was determined to be Li 10GeP 2S 12.
103
T ¬1 (K ¬1)重庆培训机构
T (°C)
l o g [ (S c m ¬1)]
σFigure 3|Thermal evolution of ionic conductivity of the new Li 10GeP 2S 12pha,together with tho of other lithium solid electrolytes,organic liquid electrolytes,polymer electrolytes,ionic liquids and gel electrolytes 3–8,13–16,20,22.The new Li 10GeP 2S 12exhibits the highest lithium ionic conductivity (12m S cm −1at 27◦C)of the solid lithium conducting membranes of inorganic,polymer or composite systems.Becau organic electrolytes usually have transport numbers below 0.5,inorganic lithium electrolytes have extremely high conductivities.
Figure 1shows the conductivity measurement results for the Li 10GeP 2S 12produced in the prent study.The conductivity was calculated from the impedance plots shown in Fig.1a,which are characteristic of pure ionic conductors;they consist of a micircle and a spike,which respectively correspond to contributions from the bulk/grain boundary and the electrode.The conductivity was obt
ained from the sum of the grain boundary and bulk resistances.The conductivity of 12mS cm −1at 27◦C is extremely high.To the best of our knowledge,this is the highest ionic conductivity reported for a lithium superionic conductor.It is comparable to or higher than the conductivities of practical organic liquid electrolytes ud in lithium-ion batteries.The activation energies for ionic conduction were calculated to be 24kJ mol −1for the temperature range of −110to 110◦C,which are typical activation energies for superionic conductors.
We evaluated the electrochemical stability from the cyclic voltammogram of a Li /Li 10GeP 2S 12/Au cell with a lithium reference electrode at a scan rate of 1mV s −1and a scan range of −0.5to 5V (Fig.1b).Cathodic and anodic currents respectively corresponding to lithium deposition (Li ++e −→Li)and dissolution (Li →Li ++e −)were obrved near 0V.No significant currents due to electrolyte decomposition were detected in the scanned voltage range.Crystalline materials with high ionic conductivities such as Li 3N and Li 1/3−x Li 3x NbO 3have low electrochemical stabilities;for example,Li 3N (ref.17)has a decomposition potential of 0.44V and La 1/3−x Li 3x NbO 3perovskite 18has a reduction potential of 1.7V.The prent Li 10GeP 2S 12has both a high ionic conductivity and a high decomposition potential.The electronic conductivity was measured by the Hebb–Wagner polarization method 19using a (−)Li /Li 10GeP 2S 12/Au(+)cell at 25◦C.The total electronic conductivi
ty (electron +hole)at the irreversible Au–Li 10GeP 2S 12interface of the asymmetric cell was calculated to be 5.70×10−9S cm −1by linear fitting between 2.8and 3.5V.
The new superionic conductor Li 10GeP 2S 12has a three-dimensional framework structure consisting of (Ge 0.5P 0.5)S 4tetrahedra,PS 4tetrahedra,LiS 4tetrahedra and LiS 6octahedra.This framework structure has a one-dimensional (1D)lithium conduction pathway along the c axis.Figure 2shows the crystal structure of Li 10GeP 2S 12.The framework is compod of (Ge 0.5P 0.5)S 4tetrahedra and LiS 6octahedra,which share a common edge and form a 1D chain along the c axis.The 1D chains are connected to one another through PS 4tetrahedra,which are connected to LiS 6octahedra by a common corner (e Fig.2b).The 1D conduction pathway is formed by LiS 4tetrahedra in the 16h and 8f sites,which share a common edge and form a 1D tetrahedron chain.The chains are connected by common corners of the LiS 4tetrahedra (Fig.2c).Neutron diffraction analysis indicates that the thermal vibration of lithium at the 16h and 8f sites is highly anisotropic (Fig.2c).The anisotropic thermal displacements indicate that lithium is displaced from the 16h and 8f sites toward interstitial positions between two 16h sites and between 16h and 8f sites.This clearly indicates the existence of 1D conduction pathways along the c axis.The occupancy parameters of 16h and 8f sites (determined respectively to be 0.691(5)and 0.643(5))indicate partially
occupied sites and show the average distribution of lithium ions along the conduction pathway,which is a characteristic of superionic conductors.
Figure 3shows the thermal evolution of the ionic conductiv-ity of the new Li 10GeP 2S 12pha together with tho of other electrolytes ud in practical batteries.For example,the organic liquid electrolyte ethylene carbonate (EC)–propylene carbonate (PC)(50:50vol.%)containing 1M LiPF 6(ref.16)has a conductivity of 10−2S cm −1at room temperature.A gel electrolyte,such as 1M LiPF 6/EC–PC (50:50vol.%)+polyvinylidene difluoride–hexafluoropropylene (10wt%;ref.20),which is currently ud in practical lithium-ion batteries to enhance their safety,has a slightly lower ionic conductivity than liquid electrolytes.Even at low temperatures,Li 10GeP 2S 12has a very high conductivity (1mS cm −1at −30◦C and 0.4mS cm −1at −45◦C),which will enable practical batteries to operate at low temperatures;this is one advantage of
make bodyCapacity (mA h g ¬1)
V o l t a g e (V )
Figure 4|Charge–discharge curves of an all-solid-state battery consisting of a LiCoO 2cathode,a Li 10GeP 2S 12electrolyte and an In metal anode.The current density is 14mA g −1.The battery has a discharge capacity of over 120mA h g −1and an excellent discharge efficiency of about 100%after th
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e cond cycle,demonstrating that Li 10GeP 2S 12is suitable as an electrolyte for all-solid-state batteries.
solid electrolytes over organic electrolytes.Many materials have been propod for overcoming the safety problems associated with high-energy-density batteries.Figure 3also shows the ionic conduc-tivities of an inorganic solid electrolyte (Li 2S–P 2S 5),an ionic liquid (1M LiBF 4/1-ethyl-3-methylimidazolium tetrafluoroborate 21)and a polymer electrolyte,LiN (CF 3SO 2)2/(CH 2CH 2O)n (n =8;ref.14).The electrolytes have conductivities that are veral orders of mag-nitude lower than tho of organic liquid electrolytes.The prent Li 10GeP 2S 12is the first electrolyte that has an ionic conductivity that is comparable to or even higher than tho of liquid organic systems and much higher chemical and thermal stabilities.
The new electrolyte Li 10GeP 2S 12was examined as a solid electrolyte for practical lithium batteries.Figure 4shows charge–discharge curves of an all-solid-state battery,which consisted of a LiCoO 2cathode,a Li 10GeP 2S 12electrolyte and an In metal anode,at a current density of 14mA g −1.The battery exhibits a discharge capacity of over 120mA h g −1and an excellent discharge efficiency of about 100%after the cond cycle,demonstrating that Li 10GeP 2S 12is applicable as a practical electrolyte for all-solid-state batteries.
In conclusion,the results prented here reveal that the new Li 10GeP 2S 12pha has an extremely high ionic conductivity that is higher than the lithium-ion conductivity of any other lithium superionic conductor.Room-temperature conductivities of 12mS cm −1are comparable to or higher than tho of organic liquid electrolytes currently ud in practical lithium-ion systems.The discovery of a new solid electrolyte will result in a wide range of fundamental studies on ionic mobility in the bulk material and this will lead to the development of next-generation batteries.Our new lithium solid electrolyte is promising for applications requiring batteries with high powers and energy densities,and for pure electric and hybrid electric vehicles and other electrochemical devices that require high safety,stability and reliability.孟晓驷
Methods
瑟缩Synthesis.The starting materials were Li 2S (Idemitsu Kosan,>99.9%purity),P 2S 5(Aldrich,>99%purity)and GeS 2(Aldrich,>99%purity).The were weighed,mixed in the molar ratio of Li 2S /P 2S 5/GeS 2to 5/1/1in an Ar-filled glove box,
placed into a stainless-steel pot and mixed for 30min using a vibrating mill (CMT,Tl-100).The specimens were then presd into pellets,aled in a quartz tube at 30Pa and heated at a reaction t
emperature of 550◦C for 8h in a furnace.After reacting,the tube was slowly cooled to room temperature.XRD (Rigaku,SmartLab and Ultima)analysis was ud to confirm the formation of a single pha.The P/Ge ratio was determined by ICP spectroscopy (iCAP,Thermo Scientific).
Crystal structure analysis.In the structural analysis process,the framework structure consisting of germanium and phosphorus sulphide polyhedra and the positions of lithium atoms were determined on the basis of synchrotron and neutron diffraction data.XRD data were obtained using a high-flux synchrotron X-ray source at the BL02B2beamline at SPring-8.A Debye–Scherrer diffraction camera was ud for the measurements at −173◦C.The specimen was aled in a quartz capillary (about 0.3mm diameter)in a vacuum for the XRD measurements.Diffraction data were collected in 0.01◦steps from 3.0◦to 70.0◦in 2θ.The incident-beam wavelength was calibrated using NIST SRM Ceria 640b CeO 2and fixed at 0.59960Å.The unit-cell parameters of the new pha were indexed using 20reflections in the XRD data and the autoindexing program DICVOL (ref.22).The validity of the space group was determined by subquent structural analysis (that is,structure modelling by the ab initio method and structural refinement by the Rietveld method).The crystal structure was solved directly by the ab initio method by global optimization of a structural model in direct space using the program FOX (ref.23).PS 4and GeS 4tetrahedra (with expected Ge–S and P–S bond lengt
hs of respectively 2.1and 2.0Åin the asymmetric unit)were ud as the building blocks in the initial configuration of the ab initio method.The program randomly moves and rotates PS 4and GeS 4tetrahedra in real space,calculates the corresponding powder diffraction pattern and arches for the best structure that reproduces the obrved diffraction pattern.The initial structure was then refined by the Rietveld method using the RIETAN-FP programme 24.The positions of some of the lithium ions were investigated by plotting a Fourier map using the synchrotron diffraction data.Neutron Rietveld analysis was carried out to accurately determine the positions and occupancy parameters of the lithium sites.The neutron diffraction data were obtained using a high-resolution neutron powder diffractometer,Super HRPD (BL08),at the neutron radiation facility centre J-PARC in Tokai,Japan.The specimen was aled in a vanadium cell (about 6mm diameter)using an indium ring.The crystal structure was refined by the Rietveld method using the Z-Rietveld programme 25.The positions of lithium ions were investigated by plotting a Fourier map and refining the positions and occupancy parameters.In the final refinement cycle,anisotropic thermal parameters were refined for all the atomic positions.Synchrotron X-ray and neutron Rietveld analysis clarified the positions of all the lithium atoms in Li 10GeP 2S 12.
Ionic and electronic conductivities.The Li 10GeP 2S 12powder was presd into a pellet (diameter 1
0mm;thickness 3–4mm)in an Ar atmosphere.It was then coated with Au to form an electrode and heated to 500◦C in a vacuum before measuring
the ionic conductivity.impedance of the Au/Li10GeP2S12/Au cell was measured between−110and110◦C in an Ar atmosphere;this was repeated two or three times by applying100–500mV in a frequency range106–10−1Hz using a frequency respon analyr(Solartron,1260).The cyclic voltammogram of the Li/Li10GeP2S12/Au cell was measured using a lithium reference with a scan rate of1mV s−1between−0.5and5.0V at25◦C.The electrical conductivity was investigated by the Hebb–Wagner polarization method19.
Charge–discharge measurements.The cathode consisted of LiNbO3-coated LiCoO2and Li10GeP2S12.The LiNbO3layer was coated on a commercial LiCoO2 powder(Toda Kogyo)using a fluidized bed granulator(MP-01,Powrex;ref.26). The LiNbO3-coated LiCoO2and Li10GeP2S12were weighed in the ratio of70:30 (wt%)and mixed using a vortex mixer for5min.The LiCoO2/Li10GeP2S12/In cell was asmbled using an indium plate(Nilaco;thickness0.1mm;diameter10mm) as an anode.The electrochemical properties of the cell
s were determined using a TOSCAT-3100(Toyo System).A cycling test was carried out between1.9and3.6V at an applied current of14mA g−1at25◦C.
Received26November2010;accepted9June2011;
published online31July2011
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This work was partially supported by a Grant-in-Aid for Scientific Rearch(A)from the Japan Society for the Promotion of Science.The synchrotron and neutron radiation experiments were carried out as projects approved by the Japan Synchrotron Radiation Rearch Institute(JASRI)(proposal No2010A1584)and the Japan Proton Accelerator Rearch Complex(J-PARC)and Institute of Materials Structure Science(proposal No 2009B0039and No.2010A0060),respectively.
Author contributions
N.K.and ived the synthesis experiments and the electrochemical characterization.K.H.,M.Y.and T.K.carried out the structural analysis.M.H.
and R.K.analyd the data and wrote the manuscript.Y.K.,S.H.and K.K.analyd the electrochemical data.A.M.carried out the synchrotron X-ray experiments. Additional information
The authors declare no competing financial interests.Supplementary information accompanies this paper on /naturematerials.Reprints and permissions information is available online at /reprints.Correspondence and requests for materials should be addresd to R.K.
