Corresponding Author

Yong-feng LIU(mselyf@zju.edu.cn)


Crystalline Li12Si7 is successfully synthesized by heating the mixture of LiH and Si with a molar ratio of 12:7, which avoids the huge difference of the melting points between Li and Si. The electrochemical performance and lithium storage mechanism of the as-prepared Li12Si7 are studied in this work. It is found that only a change in cell volume takes place without a phase change during the lithiation/delithiation of Li12Si7 at a voltage range of 0.02 ~ 0.6 V, exhibiting a solid-solution lithium storage mechanism. Such a lithium storage process effectively retards the volume effect caused by the phase change during lithiation/delithiation of Si-based anode. This induces significantly the improved electrochemical properties of crystalline Li12Si7 while cycling at 0.02 ~ 0.6 V. The first Coulombic efficiency of crystalline Li12Si7 is determined to be as high as 100%, and the capacity retention is 74% after 30 cycles, which are distinctly higher than those of Si anode (55% and 37%, respectively) under identical conditions.

Graphical Abstract


lithium-ion batteries, anode materials, Li-Si alloys, electrochemical properties, lithium storage mechanism

Publication Date


Online Available Date


Revised Date


Received Date



[1] Etacheri V, Marom R, Elazari R, et al. Challenges in the development of advanced Li-ion batteries: a review[J]. Energy & Environmental Science, 2011, 4(9): 3243-3262.

[2] Nitta N, Wu F X, Lee J T, et al. Li-ion battery materials: present and future[J]. Materials Today, 2015, 18(5): 252-264.

[3] Grande L, Paillard E, Hassoun J, et al. The Lithium/Air Battery: Still an Emerging System or a Practical Reality? [J]. Advanced Materials, 2015, 27(5), 784-800.

[4] Fotouhi A, Auger D J, Propp K, et al. A review on electric vehicle battery modelling: From Lithium-ion toward Lithium€“Sulphur[J]. Renewable and Sustainable Energy Reviews, 2016, 56: 1008-1021.

[5] Abada S, Marlair G, Lecocq A, et al. Safety focused modeling of lithium-ion batteries: A review[J]. Journal of Power Sources, 2016, 306: 178-192.

[6] Zhang W J. A review of the electrochemical performance of alloy anodes for lithium-ion batteries[J]. Journal of Power Sources, 2011, 196(1): 13-24.

[7] Ji L W, Lin Z, Alcoutlabi M, et al. Recent developments in nanostructured anode materials for rechargeable lithium-ion batteries[J]. Energy & Environmental Science, 2011, 4(8): 2682-2699.

[8] Yang Y, Jeong S, Hu L, et al. Transparent lithium-ion batteries[J]. Proceedings of the National Academy of Sciences of the United States of America, 2011, 108(32): 13013-13018.

[9] Park C M, Kim J H, Kim H, et al. Li-alloy based anode materials for Li secondary batteries[J]. Chemical society reviews, 2010, 39(8): 3115-3141.

[10] Liang B, Liu Y P, Xu Y H. Silicon-based materials as high capacity anodes for next generation lithium ion batteries[J]. Journal of Power Sources, 2014, 267: 469-490.

[11] Ryu J H, Kim J W, Sung Y E, et al. Failure modes of silicon powder negative electrode in lithium secondary batteries[J]. Electrochemical and solid state letters. 2004, 7(10), A306-A309.

[12] Obrovac M N, Krause L J. Reversible cycling of crystalline silicon powder[J]. Journal of the electrochemical society, 2007, 154(2), A103-A108.

[13] Tian H J, Tan X J, Xin F X, et al. Micro-sized nano-porous Si/C anodes for lithium ion batteries[J]. Nano Energy, 2015, 11: 490-499.

[14] Liu Y F, Yan P, Ma R J, et al. Electrochemical properties of the ternary alloy Li5AlSi2 synthesized by reacting LiH, Al and Si as an anodic material for lithium-ion batteries[J]. Journal of Power Sources, 2015, 283: 54-60.

[15] Ma R J, Liu Y F, Yang Y X, et al. Mg2Si anode for Li-ion batteries: Linking structural change to fast capacity fading[J]. Applied physics letters, 2014, 105: 213901-1-4.

[16] Yan J M, Huang H Z, Zhang J, et al. The study of Mg2Si/carbon composites as anode materials for lithium ion batteries[J]. Journal of Power Sources, 2008, 175(1): 547-552.

[17] Liu Y F, Ma R J, He Y P, et al. Synthesis, structure transformation, and electrochemical properties of Li2MgSi as a novel anode for Li-lon Batteries[J]. Advanced functional materials, 2014, 24(25): 3944-3952.

[18] Liu L, Obrovac M N. Structural changes in LiAlSi during electrochemical cycling[J]. ECS Electrochemistry Letters, 2012, 1(1): A10-A12.

[19] Lacroix-Orio L, Tillard M, Belin C. Synthesis, crystal and electronic structure of Li13Ag5Si6, a potential anode for Li-ion batteries[J]. Solid State Sciences, 2008, 10(1): 5-11.

[20] Spina L, Jia Y Z, Ducourant B, et al. Compositional and structural variations in the ternary system Li-Al-Si[J]. Zeitschrift fur Kristallographie, 2003, 218(11): 740-746.

[21] Alcántara R, Tillard-Charbonnel M, Spina L, et al. Electrochemical reactions of lithium with Li2ZnGe and Li2ZnSi[J]. Electrochimica Acta, 2002, 47(7): 1115-1120.

[22] Hwang C, Park J. Electrochemical properties of Si-Ge-Mo anode composite materials prepared by magnetron sputtering for Lithium ion batteries[J]. Electrochimica Acta, 2011, 56(19): 6737-6747.

[23] Wang J, Du N, Zhang H, et al. Cu-Si1-xGe core-shell nanowire arrays as three-dimensional electrodes for high-rate capability lithium-ion batteries[J]. Journal of Power Sources, 2012, 208: 434-439.

[24] Ma R J, Liu Y F, He Y P, et al. Chemical preinsertion of lithium: an approach to improve the intrinsic capacity retention of bulk Si anodes for Li-ion batteries[J]. Journal of Physical Chemistry Letters, 2012, 3(23): 3555-3558.

[25] Liu Y F, He Y P, Ma R J, et al. Improved lithium storage properties of Mg2Si anode material synthesized by hydrogen-driven chemical reaction[J]. Electrochemistry communications, 2012, 25: 15-18.

[26] Li J, Dahn J R. An in situ X-ray diffraction study of the reaction of Li with crystalline Si[J]. Journal of the Electrochemical Society, 2007, 154(3): A156-A161.

[27] Liu X H, Zhang L Q, Zhong L, et al. Ultrafast electrochemical lithiation of individual Si nanowire anodes[J]. Nano Letters, 2011, 11(6): 2251-2258.

[28] Wang C, Li X, Wang Z, et al. In situ TEM investigation of congruent phase transition and structural evolution of nanostructured silicon/carbon anode for lithium ion batteries[J]. Nano Letters, 2012, 12(3): 1624-1632.

[29] McDowell M T, Lee S W, Harris J T, et al. In situ TEM of two-phase lithiation of amorphous silicon nanospheres[J]. Nano Letters, 2013, 13(2): 785-764.

[30] Zhang T, Gao J, Fu L J, et al. Natural graphite coated by Si nanoparticles as anode materials for lithium ion batteries[J]. Journal of Materials Chemistry, 2007, 17(13): 1321-1325.

[31] Liu X H, Zhong L, Huang S, et al. Size-dependent fracture of silicon nanoparticles during lithiation[J]. ACS Nano, 2012, 6(2): 1522-1531.

[32] Wang J W, He Y, Fan F, et al. Two-phase electrochemical lithiation in amorphous silicon[J]. Nano Letters, 2013, 13(2): 709-715.

[33] Lee S W, McDowell M T, Berla L A, et al. Fracture of crystalline silicon nanopillars during electrochemical lithium insertion[J]. Proceedings of the National Academy of Sciences of the United States of America, 2012, 109(11): 4080-4085.

[34] Zhao K, Pharr M, Wan Q, et al. Concurrent reaction and plasticity during initial lithiation of crystalline silicon in lithium-ion batteries[J]. Journal of the Electrochemical Society, 2012, 159(3): A238-A243.

[35]Liu X H, Fan F, Yang H, et al. Self-limiting lithiation in silicon nanowires[J]. ACS Nano, 2013, 7(2): 1495-1503.



To view the content in your browser, please download Adobe Reader or, alternately,
you may Download the file to your hard drive.

NOTE: The latest versions of Adobe Reader do not support viewing PDF files within Firefox on Mac OS and if you are using a modern (Intel) Mac, there is no official plugin for viewing PDF files within the browser window.