Solid state silicon battery

A solid state silicon battery or silicon anode all solid state battery is a type of rechargeable lithium ion battery consisting of a solid electrolyte, solid cathode, and silicon based solid anode.[1][2]

In solid state silicon batteries, lithium ions travel through a solid electrolyte from a positive electrode to a negative silicon electrode. While silicon anodes for lithium ion batteries have existed in theory for a long time, they have been largely dismissed as infeasible due to general incompatibility with liquid electrolytes. Developments in 2021 have proven that solid state silicon lithium ion batteries are possible, and have many of the benefits that they were believed to have.[1] All solid state silicon batteries use a solid electrolyte that more easily interfaces with the silicon anode to utilize the full efficiency of silicon in energy storage. These batteries are different from other solid state batteries due to their use of silicon instead of less energy dense compounds.[1]

Silicon is a difficult anode material to work with because of the volumetric expansion of silicon over 300% experienced during lithiation (also known as lithium intercalation) . This contributes to the other major difficulty; lithium loss due to buildup within the battery.[1][3]

History

Lithium-ion batteries were first proposed in a French patent from 1949. Research and development of lithium-ion batteries began in the 1960s. These batteries initially used organic liquid electrolytes, but there were two main issues: organic electrolytes and lithium metal were unstable, and the growth of dendrites during cycling which could lead to short circuiting. In the 1980s, two solutions were proposed. One of the amendments to the batteries was to replace the lithium metal with some other material that could transfer lithium ions at lower temperatures and with more stability. This method continues to be the principle behind lithium-ion batteries used today. The other method was to use a solid electrolyte instead of a liquid one. Research into this solution lead to the development of the first rechargeable all-solid-state lithium metal batteries.[4]

Silicon anode batteries are common in the ideas about possible alternative anode lithium-ion batteries. Silicon anodes have a theoretical energy density of 4200 mAh/g,[2] a density almost 10 times the 372 mAh/g of current graphite-based lithium ion batteries.[3] However, they also have a reputation for degradation in liquid electrolytes and issues with expansion and contraction during energy transfer. Some attempts to mitigate these prohibitive downsides involve changing the structure of the anode by sacrificing some density for more stable compounds. Other attempts to mitigate the issues with liquid electrolytes involve the same principles of replacing or changing some of the electrolyte for more efficient interfacing. The largest issue with silicon the trapping of lithium ions in the anode.[1] Because of the difficulties of silicon anodes, commercial application of silicon anodes in lithium batteries had been all but abandoned.[5][6]

New literature concerning both silicon anode and all-solid-state batteries combines the two. Using a solid electrolyte and a microsilicon lattice electrode enables high energy density, low capacity degradation over hundreds of charging cycles, and lower charging temperatures.[1]

Design

A lab prototype silicon anode solid state battery was developed by collaboration between engineers from University of California San Diego and researchers from LG Energy Solutions.[5] Their technology utilizes sulfate solid-state electrolytes (SSE) to stabilize and allow for the use of a 99.9% weight μSi anode. This limits the volumetric changes of the silicon anode during lithiation and loss of lithium to growths in the liquid electrolyte. Their work utilizes the μSi in battery cells consisting of μSi, a solid state electrolyte, and lithium nickel cobalt manganese oxide. The use of a solid state electrolyte reduces the contact of the μSi with the electrolyte to a flat surface. The flat surface alongside a carbon-free design makes the spreading of Li-Si more reversible. The use of a non-metallic lithium source eliminates the high temperature requirements that metallic lithium batteries require to charge.[1]

Interface Structure

In batteries with solid lithium metal electrodes, charging generally requires high temperatures. This limits the use of lithium metal batteries. To allow lower charging temperatures and better interfacing, the UCSD and LG battery uses μSi||SSE||lithium nickel cobalt manganese oxide (NCM811 - LiNi0.8Co0.1Mn0.1O2). While liquid electrode batteries have a 3 dimensional contact between the electrode and the electrolyte silicon is conductive enough to allow for a single plane of contact. The interface of the SSE and the μSi electrode stays a single plane during the volumetric change caused by lithium intercalation. A single plane prevents the multi-angled interfaces that cause structural failure in previous silicon anode batteries.[1]

The collaborative work between the University of California San Diego and LG Energy Solutions is the first demonstration of a silicon all-solid-state battery.[5][6]

Anode Composition

Typical lithium-ion batteries use an anode containing carbon, between 20 and 40 percent by weight for existing silicon mixtures. Sometimes this is a full graphite anode, and other times it just has carbon additives. In a test utilizing NCM811 as the cathode, the carbon anode had an initial voltage plateau of 2.5V. The carbon-free silicon anode in the same test had an initial voltage plateau of 3.5V.[1]

Utilizing an anode without carbon is important to keeping the SSE from undergoing electrochemical decomposition. The carbon anode also saw a large build up of the solid electrolyte interphase (SEI), an undesirable result of the electrolyte decomposing. In the carbon-free battery, the SEI stabilizes very quickly. Lithium Phosphorus Sulfide Chloride gets reduced to form products that do not react nearly as much. The SEI is stable after the reduction equation.

The largest focus with silicon all-solid-state batteries is to reduce the losses of power and lifetime for batteries.[1]

References
  1. Tan, Darren H. S.; Chen, Yu-Ting; Yang, Hedi; Bao, Wurigumula; Sreenarayanan, Bhagath; Doux, Jean-Marie; Li, Weikang; Lu, Bingyu; Ham, So-Yeon; Sayahpour, Baharak; Scharf, Jonathan (2021-09-24). "Carbon-free high-loading silicon anodes enabled by sulfide solid electrolytes". Science. 373 (6562): 1494–1499. Bibcode:2021Sci...373.1494T. doi:10.1126/science.abg7217. PMID 34554780. S2CID 232147704.
  2. Miyazaki, Reona (2020). "High-Capacity Anode Materials for All-Solid-State Lithium Batteries". Frontiers in Energy Research. 8: 171. doi:10.3389/fenrg.2020.00171. ISSN 2296-598X.
  3. Higgins, Thomas M.; Park, Sang-Hoon; King, Paul J.; Zhang, Chuanfang (John); McEvoy, Niall; Berner, Nina C.; Daly, Dermot; Shmeliov, Aleksey; Khan, Umar; Duesberg, Georg; Nicolosi, Valeria (2016-03-08). "A Commercial Conducting Polymer as Both Binder and Conductive Additive for Silicon Nanoparticle-Based Lithium-Ion Battery Negative Electrodes". ACS Nano. 10 (3): 3702–3713. doi:10.1021/acsnano.6b00218. hdl:2262/77389. ISSN 1936-0851. PMID 26937766.
  4. Guyomard, Dominique; Tarascon, Jean-Marie (1994). "Rocking-chair or lithium-ion rechargeable lithium batteries". Advanced Materials. 6 (5): 408–412. doi:10.1002/adma.19940060516. ISSN 1521-4095.
  5. Patringenaru, Ioana. "A New Solid-state Battery Surprises the Researchers Who Created It". ucsdnews.ucsd.edu. Retrieved 2021-10-21.{{cite web}}: CS1 maint: url-status (link)
  6. Dent, S. "Solid-state silicon batteries could last longer and charge faster". Engadget. Retrieved 2021-10-21.{{cite web}}: CS1 maint: url-status (link)
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