Electrochimica Acta 52 (2006) 15761581

Relationship between glass network structure and conductivity of Li2OB2O3P2O5 solid electrolyte
Kang Ill Cho a , Sun Hwa Lee a , Dong Wook Shin a, , Yang Kuk Sun b
a

Division of Material Science and Engineering, Hanyang University, Seoul 133-791, South Korea b Division of Applied Chemical Engineering, Hanyang University, Seoul 133-791, South Korea

Received 28 October 2005; received in revised form 6 February 2006; accepted 24 February 2006 Available online 30 May 2006

Abstract Solid state glass electrolyte, xLi2 O-(1 x)(yB2 O3 -(1 y)P2 O5 ) glasses were prepared with wide range of composition, i.e. x = 0.35 0.5 and y = 0.17 0.67. This material system is one of the parent compositions for chemically and electrochemically stable solid-state electrolyte applicable to thin lm battery. Lithium ion conductivity of Li2 OB2 O3 P2 O5 glasses was studied in the correlation to the structural variation of glass network by using FTIR and Raman spectroscopy. The measured ionic conductivity of the electrolyte at room temperature increased with x and y. The maximum conductivity of this glass system was 1.6 107 1 cm1 for 0.45Li2 O0.275B2 O3 0.275P2 O5 at room temperature. It was shown that the addition of P2 O5 reduces the tendency of devitrication and increases the maximum amount of Li2 O added into glass former without devitrication. As Li2 O and B2 O3 contents increased, the conductivity of glass electrolyte increased due to the increase of three-coordinated [BO3 ] with a non-bridging oxygen (NBO). 2006 Elsevier Ltd. All rights reserved.
Keywords: Glass electrolyte; Li-ion battery; Thin lm battery; Lithiumborophosphate

1. Introduction Lithium based solid electrolytes are of considerable interest recently since it is required to fabricate the thin lm battery as well as to reduce the problem of harmful chemical reaction between liquid type electrolyte and active electrode materials. Despite immediate commercialization is far from realization, thin lm battery is actively pursued due to its various emerging applications such as smart card, self-sustaining memory devices, and bio-medical appliances. Among the various candidates for solid electrolyte of thin lm battery, the inorganic glasses are one of the frequently mentioned materials. Oxide glasses have long been studied intensively since those materials exhibit relatively stable chemical properties and can be easily fabricated into thin lm. Many researchers have studied to improve the low ionic mobility of inorganic oxide glasses, which turned out not to be great success. The approaches to improve the ionic conductivity of oxide glass are divided into two categories; the increase

Corresponding author. Tel.: +82 2 2220 0503; fax: +82 2 2292 3851. E-mail address: dwshin@hanyang.ac.kr (D.W. Shin).

of number of mobile ions and the increase of the mobility of ions. The number of mobile ion is simply increased by adding more Li2 O into glass former network, nevertheless the number of truly mobile ion is not linearly dependent on the added Li2 O. The lithium ion mobility is determined by two factors; the free volume of glass network and the local dielectric environment. The rst one determines mainly the activation energy of ionic drift under an electric eld and the second one determines the driving force of ionic motion through local eld effect. The free volume of glass network is affected by various parameters such as the network structure varying with the chemical composition, thermal history, and fabrication method, so on. The mixed anion effect contributes to mainly the increase of free volume and the addition of highly polarizable cations contributes to the local eld effect. Fast ionic conducting borate glasses in which lithium ions are the mobile species are usually represented by the xLi2 O(1 x)B2 O3 . Lithium oxide and boron oxide are the glass network modier and glass former respectively. According to Krogh-Moe [1], the structure of pure vitreous B2 O3 consists of a random network of boroxol rings and BO3 triangles connected by B O B linkage (bridging oxygen atom). The addition of alkali oxides modies the boroxol ring; complex borate groups

0013-4686/$ see front matter 2006 Elsevier Ltd. All rights reserved. doi:10.1016/j.electacta.2006.02.065

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with one or two four-coordinated boron atoms are formed [2]. Bray et al. [3] have studied the coordination change of boron atom by nuclear magnetic resonance (NMR). They found an increase in the fraction of boron atoms in four-coordination up to x = 0.7. The number of four-coordinated boron atoms then decreases, and they have explained this behavior by the formation of BO3 groups with non-bridging oxygen (NBO). In this study, the structural variation of the oxide amorphous electrolytes of Li2 OB2 O3 P2 O5 system was investigated by Fourier transform infrared spectroscopy and Raman spectroscopy to nd out the correlation with the electrical conductivity. 2. Experiments Glass electrolytes with composition xLi2 O-(1 x)(yB2 O3 (1 y)P2 O5 ) were prepared from reagents grade material (99% Li2 CO3 , 98% P2 O5 and 95% B2 O3 ). The starting materials were mixed in proportions appropriate to form 30 g batches. Each batch was melted at 1000 C for 6 h in Pt crucibles in an electrically heated furnace. The amorphous state of glass electrolytes was identied at room temperature by X-ray diffraction (XRD). Pt lm was sputtered on both sides of the glass electrolyte as ion blocking electrodes to measure the ionic conductivities. Conductivity was measured by complex impedance method using IM6 impedance analyzer with an ac voltage of 50 mV amplitude over the frequency range 1 Hz1 MHz at room temperatures. The activation energy of Li+ ionic conduction were measured by the temperature dependence of the conductivity in the temperature range of 25200 C. The correlation between the structural modication of glass network and conductivity was characterized by FTIR and Raman spectroscopy as a function of the chemical composition. Glasses were ground, mixed with KBr in a 1:100 weight ratio and pressed into pellets to obtain the infrared spectra (IR Spectroscopy: Magna-IR 760 Spectrometer) in the range from 400 to 4000 cm1 . IR transmittance was measured rst and converted to reectance using KramersKronig relationship. The Raman spectra of the glasses were performed using a laser Raman Spectrophotometer (JASCO NRS-3100) and a conventional counting system in 4001800 cm1 range under air atmosphere. 3. Results and discussion Fig. 1(a) shows a typical Nyquist plot of the xLi2 O(1 x)(0.5B2 O3 0.5P2 O5 ) glass system at room temperature and Fig. 1(b) presents the conductivity variation with mole fraction of network modier, Li2 O. As shown in Fig. 1(b), the lithium-ion conductivity of glasses is enhanced as network modier contents increase up to x = 0.47 due to the increase in both lithium ion concentration and non-bridging oxygen. Non-bridging oxygen site is known to offer the hoping site for ionic conduction in oxide glass network where cation such as Li+ jumps into or out easily due to relatively weak bonding or shallow energy well [4]. The formation of non-bridging oxygen is also contributing to the formation of relatively open network structure with large free volume for ion drift. The combination

Fig. 1. The variation of conductivity by the addition of Li2 O. (a) Nyquist plots of xLi2 O-(1 x)(0.5B2 O3 0.5P2 O5 ) glass electrolyte. (Amplitude: 50 mV, frequency range:10 Hz1 MHz, at room temperature). (b) Conductivity as a function of Li2 O concentration.

of these two effects increases the ionic conduction of glass electrolyte. The variation of non-bridging oxygen content was investigated by FTIR spectra, which is summarized in Fig. 2(a). The reectance peak around 1170 cm1 is assigned to B O bond stretching of trigonal BO3 with a non-bridging oxygen [5]. In Fig. 2(a), one can see that this peak grows as the concentration of Li2 O increases. The increase of non-bridging oxygen is accompanied by the formation of BO3 trigonal unit since, at high Li concentration, the addition of Li2 O converts the BO4 tetrahedral unit to BO3 trigonal unit with a non-bridging oxygen as described by the following reaction equation;

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Fig. 2. The variation of FTIR spectra by the addition of Li2 O. (a) FTIR reectance spectra of xLi2 O-(1 x)(0.5B2 O3 0.5P2 O5 ) system glass electrolyte at various Li2 O concentration. (b) The variation of the ratio between peak height of 990 cm1 band and 1300 cm1 band [9] in Fig. 4 (a). The peak height ratio is compared to the number of four-coordinated boron. Li2 O and B2 O3 are represented in mol%.

In Fig. 2(b), the fraction of four-coordinated boron is compared as a function of Li2 O/B2 O3 ratio to the ratio of peak height between 990 cm1 band and 1300 cm1 band. The peak height ratio roughly follows the variation of four-coordinated boron which means that the relative fraction of four-coordinated boron was actually reduced dramatically as Li2 O concentration increased, although the absolute peak height of 990 cm1 band was not varied noticeably. This result is in good agreement with the previous report [5] that the relative fraction of trigonal BO3 with a non-bridging oxygen increases as the concentration of Li2 O increases while that of four-coordinated boron reduces. The conversion from four-coordinated boron to three-coordinated boron with a non-bridging oxygen can be also veried by the growth of the peak at 1200 cm1 which is unfortunately not clear in the specimen used in this work due to large peak around 12501400 cm1 . However, the growth of 1200 cm1 peak with increasing Li2 O becomes apparent at high B2 O3 concentration where the left shoulder of 12501400 cm1 becomes taller.

Fig. 3. The variation of Raman spectra by the addition of Li2 O. (a) Raman reectance spectra of xLi2 O-(1 x)(0.5B2 O3 0.5P2 O5 ) system glass electrolyte at various Li2 O concentration. (b) The shift of the band between peak of 1060 cm1 and 1010 cm1 with concentration of Li2 O increase in the system.

The experimental evidence of the conversion from fourcoordinated boron BO4 or (BO2 ) to trigonal BO3 is also found in the Raman spectra summarized in Fig. 3. Fig. 3(a) presents the variation of Raman spectra as a function of mole fraction of network modier Li2 O. The peak around 630 cm1 is assigned to the vibration of (BO2 ) groups in pure alkali borate glass [6]. But in the alkali borophosphate glasses, it has a different assignment. Previous report [7] has attributed it to the vibration of (BO2 ) groups with P O , while Villa et al. [8] argued that it came from the contribution of P O B mode. Though minor shift in peak position due to the presence of phosphate groups seems to be found in borophosphate glass, it is certain that the 620630 cm1 band is closely related to the presence of BO4 or (BO2 ) units. The peak around 730 cm1 was assigned to the vibration of diborate groups (B4 O7 )2 , which is a combination of trigonal boron and tetragonal boron [6].

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phosphorus and contains a non-bridging oxygen, which is represented by the following formula:

The peak at 1110 cm1 is assigned to the overlapping of various phosphate groups with non-bridging oxygen and (B O P)0 group. The relative peak height at 1010 cm1 grew noticeably compared to that of 630, 730, 1110 cm1 as the Li2 O concentration increased and this result suggests that the tetragonal boron unit BO4 converts to trigonal boron BO3 with a non-bridging oxygen and many (B O P)0 group converted to (B O P) group by the addition of Li2 O [9]. The peak position of 10101060 cm1 band as a function of Li2 O content is shown in Fig. 3(b). This result means that Li2 O enhances the depolymerization of (PO)n n chains by the formation of non-bridging oxygen and results in the formation of (P4 O13 )6 , (P3 O10 )5 and

Fig. 4. The variation of conductivity and FTIR spectra by the addition of P2 O5 . (a) Conductivity as a function of B2 O3 concentration at x = 0.4, (b) FTIR reectance spectra of xLi2 O-(1 x)(yB2 O3 (1 y)P2 O5 ) glass electrolyte at various B2 O3 concentration.

In Fig. 3(a), one can see that 1060 cm1 peak shifted to 1010 cm1 and the peak height grows markedly as the concentration of Li2 O increases. This characteristic peak is attributed to the overlapping of peaks due to (B O P) and (PO3 )n n chains. (B O P) is the combination of trigonal boron and tetragonal

Fig. 6. The variation of ratio between peak height of 980 cm1 band and 1180 cm1 band in Fig. 5(b). Li2 O and B2 O3 are represented in mol%.

Fig. 5. Structure of the Li2 OB2 O3 P2 O5 glass.

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(P2 O7 )4 groups [9]. In overall, the addition of Li2 O induces the structural disintegration through the formation of non-bridging oxygen and the electrical conductivity increases accordingly due to easier motion of lithium ion in glass network. Fig. 4(a) presents the conductivity variation with mole fraction of network former, B2 O3 . In this gure, the lithium-ion conductivity is enhanced as network former (B2 O3 ) contents increase up to x = 0.4. The increment of y or B2 O3 /P2 O5 ratio can be conrmed from the IR reection peak at 12501400 cm1 in Fig. 4(b), which is assigned to the harmonic vibrations of boroxol rings. The peak becomes taller since the boroxol rings become abundant as the B2 O3 /P2 O5 ratio increases. The peak at approximately 1180 cm1 , the stretching band of BO3 with a non-bridging oxygen, showed the minimum at y = 0.42 and the maximum at y = 0.67. This result suggests that the proportion of four-coordinated boron, BO4 , is maximized at y = 0.42 or B2 O3 /P2 O5 ratio = 1. The four-coordinated boron, BO4 , is

formed by the reaction depicted in Fig. 5. The non-bridging oxygen located at double bond in P2 O5 tetrahedron easily reacts with one of BO3 arm with a non-bridging oxygen to form two tetrahedrons and this effect would be maximized at B2 O3 /P2 O5 ratio 1 for the statistical reason as shown in Fig. 6. Fig. 6 presents the ratio between peak height of 980 cm1 band and 1180 cm1 band as a function of the ratio of mole fraction of network former, B2 O3 /P2 O5 . The peak height ratio shows the minimum at B2 O3 /P2 O5 1 which means that the ratio between four-coordinated boron BO4 and three-coordinated boron BO3 with a non-bridging oxygen is minimized at this proportion of network former. Fig. 7(a) presents the variation of Raman spectra of 0.4Li2 O0.6(yB2 O3 (1 y)P2 O5 ) with mole fraction of network former B2 O3 . In this gure, the 1170 cm1 strong peak is assigned to the vibration of PO4 unit [10]. It is natural that the 1170 cm1 peak is very strong due to high concentration of P2 O5 at low B2 O3 concentration. This peak gradually weakened as the concentration of B2 O3 increased, while the peak at 1110 cm1 , the overlapped peak of various phosphate group and the (B O P)0 unit, started to grow and eventually converted to 1030 cm1 peak, the overlapped peak of various phosphate group and the (B O P) unit. In Fig. 7(b), this result shows that change from (B O P)0 with accompany (P4 O13 )6 and (P3 O10 )5 groups to (B O P) with (P2 O4 )4 groups causes a shift of peak position as the concentration of B2 O3 increase [9]. The peak at 710 cm1 also weakened markedly as the concentration of B2 O3 increased, while the peak at 630 cm1 grew. This result indicates that the proportion of trigonal boron units decreased since the ratio Li2 O/B2 O3 became lower or the proportion of Li+ ion bonded to boron units decreased as the concentration of B2 O3 increased. 4. Conclusions Solid state glass electrolytes, xLi2 O-(1 x)(yB2 O3 (1 y)P2 O5 ), prepared by melt quenching method. P2 O5 was added into binary Li2 OB2 O3 glass electrolyte as a network former to prevent the devitrication and help the stable formation of amorphous phase of the glass electrolyte. The addition of P2 O5 successfully widened the glass-forming region to the regime of higher concentration of lithium. However, the addition of P2 O5 was not benecial for the electrical conduction. P2 O5 converted the three-coordinated [BO3 ] with a non-bridging oxygen into four-coordinated boron eliminating non-bridging oxygen sites, which reduces the electrical conductivity of Li+ in glass electrolyte. In other hand, as B2 O3 contents increased, the conductivity of glass electrolyte increased due to the increase of three-coordinated [BO3 ] with a non-bridging oxygen. The maximum ionic conductivity was achieved with 1.6 107 S/cm at room temperature. The conductivity was not high enough for the application as a bulk type electrolyte. However, the Li2 OB2 O3 P2 O5 system is believed to be one of the good candidate for thin lm solid electrolyte due to its stable glass forming ability and stable chemical properties.

Fig. 7. The variation of Raman spectra by the addition of B2 O3 . (a) Raman reectance spectra of 0.4Li2 O-0.6(yB2 O3 (1 y)P2 O5 ) glass electrolyte at various B2 O3 concentration. (b) The shift of the band between peak of 1170 and 1030 cm1 with concentration of B2 O3 increase in the system.

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Acknowledgments This work was supported by the Ministry of Information & Communications, Korea, under the Information Technology Research Center (ITRC) Support Program. References
[1] A. Levasseur, J.C. Brethous, J.M. Reau, P. Hagenmuller, Mater. Pes. Bull. 6 (1966) 46.

[2] R.L. Mozzi, B.E. Warren, J. Appl. Crystallogr. 3 (1970) 251. [3] P.J. Bray, S.A. Feller, G.E. Jekkison Jr., Y.H. Yum, J. Non-Cryst. Solids 38-39 (1980) 98. [4] A. Krol, W. Nazarewicz, Mat. Sci. Eng. B 3 (1989) 307. [5] A. Bunde, M.D. Ingram, P. Maass, K.L. Ngai, J. Phys. A 24 (1992) L881. [6] W. Konijnendijk, Philips Res. Repts. (Suppl. 1) (1975). [7] T. Tsuchiya, T. Moriya, J. Non-Cryst. Solids 3839 (1980) 323. [8] M. Villa, G. Chiodelli, M. Scagliotti, Solid State Ionics 1819 (1986) 382. [9] J. Yifen, C. Xiangsheng, H. Xihuai, J. Non-Cryst. Solids 147150 (1989) 112. [10] G.S. Park, E.T. Kang, J. Korean Ceram. Soc. 373380 (1993) 30.