What Is a Solid State Battery Made of

Solid State Battery

From: Chalcogenide Glasses , 2014

SECONDARY BATTERIES – LITHIUM RECHARGEABLE SYSTEMS | Electrolytes: Solid Sulfide

R. Kanno , in Encyclopedia of Electrochemical Power Sources, 2009

Composite interface – Graphite/SE interface

Solid-state batteries with two kinds of lithium solid electrolytes showed good characteristics for the graphite electrode. The electrolyte is a combination of Li–Li₂S–P₂S₅ glass contacted with the negative electrode material and Li₃PO₄–Li₂S–SiS₂ glass or Li₂S–GeS₂–P₂S₅ crystalline material contacted with the positive electrode. The former electrolyte was stable to electrochemical reduction, and the latter two to oxidation. This combination made it possible to use graphite as the negative electrode. The energy density of the LiCoO₂/SE1/SE2/C battery is comparable to that of commercialized Li-ion batteries.

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Electrodes

Aditi Sengupta , in Metal Oxide Glass Nanocomposites, 2020

13.3.1 Nanosized transition-metal oxides as negative electrode materials for lithium ion batteries

Solid state batteries have been considered an important source of power for a wide variety of applications for a long period of time, and in particular, lithium-ion batteries are coming out as the technology of selection for portable electronics [9, 10]. One of the top most challenges in the design of these batteries is to make sure that the electrodes maintain their integrity and quality over many discharge-recharge cycles. Although emerging electrode systems have recently been proposed, their lifespans are limited by Li-alloying agglomeration or the increase of passivation layers, which stop the complete reversible insertion of Li ions into the negative electrodes. Electrodes made of nanoparticles of transition-metal oxides (MO, where M is Co, Ni, Cu, or Fe) demonstrate electrochemical capacities of 700 mA h/g, with 100% capacity retention for up to 100 cycles and high recharging rates. The mechanism of Li reactivity is different from the classical Li insertion/deinsertion or Li-alloying processes, and related with the formation and decomposition of Li₂O, with the reduction and oxidation of metal nanoparticles (in the range 1–5 nm) respectively. It is expected that the use of transition-metal nanoparticles to increase surface electrochemical reactivity will lead to further improvements in the performance of lithium-ion batteries [11].

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Overview of batteries for future automobiles

P. Kurzweil , J. Garche , in Lead-Acid Batteries for Future Automobiles, 2017

2.6.3 All-solid-state lithium batteries

Solid-state batteries are an emerging option for next-generation traction batteries promising low cost, high performance and high safety [50,51]. Liquid electrolytes with high ionic conductivity (∼10 ⁻³ S cm⁻¹ at room temperature) and practically no electronic conductivity, perform effectively over a wide temperature range (from few tens of degrees below 0°C to about 100°C). But they pose disadvantages: high flammability, highly resistive SEI at the electrodes leading to capacity loss, electrolytic decomposition at high voltages limiting the use of high voltages cathode materials, formation of HF at thermal runaway, and risk of leakage. Solid electrolyte lithium-ion cells do not show these drawbacks and allow higher operating temperatures due to better thermal stability. Due to higher electrochemical stability, high potential cathodes and even metallic Li may be used as anode leading to a higher specific energy. However, lithium melts at ∼180°C.

State-of-the-art. At present, the solid state technology concentrates on small cells due to the production costs. The coin cell (20 mm diameter, 1 mm thick, 85 mAh) of Infinite Power Solutions, Inc., and Sakti3 reached energy densities above 1000 Wh L⁻¹ [52]. About 20 companies worldwide succeeded in prototype manufacturing. The solid-state technology offers opportunities for large cells and EV applications. The 'Batscap' of Bolloré uses a Li-metal anode, a V₂O₅ cathode and a PEO-LiTFSI polymer electrolyte; the 2.7 kWh module yields 31 V, 25 kg, 25 L, P_max: 8 kW, 110 Wh/kg. Ten modules form the 27 kWh battery in the 'Blue Car', having a range of ca. 250 km and a recharge time of 6 h. About 3000 cars are in use [53]. Since solid systems do not require any cooling system, they weigh less and require less space than lithium-ion batteries for powering electric automobiles. Volkswagen acquired a 5% stake in US QuantumScape, and Bosch purchased US Seeon; both US companies are developing polymer systems. Toyota is working at all-solid cells with ceramic electrolytes. The 2 Ah model cell (C/Li2S-P2S5/NCM) reached about 400 Wh L⁻¹ and 250 W L⁻¹.

Materials. The cell chemistry of all-solid state cells is in general the same as of liquid electrolyte cells. Anode materials comprise carbon, titanates, Li-alloys and metallic lithium; cathode materials are Li-based oxides (LCO, NCA), and phosphates (LFP), vanadium oxide [51] and future microstructural 5 V materials. As polymer electrolytes, mainly PEO with conducting salts such as [LiCF₃SO₂)₂N] (LiTFSI) is used. As ceramic electrolytes especially LiPON, Li₁₀GeP₂S₁₂ or Li₂S-P₂S₅ are possible.

Challenges. The ionic conductivity of polymer electrolytes (10⁻⁶…10⁻⁵ S cm⁻¹) at room temperature is poor (Fig. 2.13); moderate Li-ion conductivity is reached at 60–100°C. Solid ceramic electrolytes (10⁻⁴ to 10⁻³ S cm⁻¹) come close to liquid organic electrolytes but suffer from the poor contact between solid electrolyte and solid electrode interphase, and the grain boundary resistance, which often dominates the bulk resistance. To overcome these effects, thin-film cells are developed with about 0.1 mm thickness, which is one tenth of the thickness of the thinnest prismatic liquid electrolyte Li-ion cell. Hybrid electrolytes consist of solid-state electrolyte and a small amount of liquid electrolyte.

Specific power density of all-solid cells is low compared with liquid electrolytes. Cost for small cells in the range of 25,000 result from expensive processing by atomic layer deposition (ALD). Cheap nonvacuum manufacturing processes are under development, promising 100 US$ kWh^-1.

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Background of energy storage

Suresh Sagadevan , ... Jiban Podder , in Advances in Supercapacitor and Supercapattery, 2021

1.9.3 Solid-state battery R&D

Li-ion solid-state batteries are Li-ion batteries that use solid electrolyte materials. Solid-state batteries have excellent safety efficiency, high energy density, and a wide variety of operating temperatures. Many scientists are hoping to apply this technology to the next generation of Li-ion batteries, given these advantages. This has prompted research to create strong and quasi-solid electrolytes. Some study teams are working to enhance the compatibility of solid-state electrolytes, standard cathode materials, and metallic lithium anodes, all while inhibiting the development of lithium dendrites in these installations. Others focus on building high-quality energy and stable Li-ion battery systems for the solid-state cycle. Gel-type electrolyte materials have also become a significant topic of studies into materials science. Because solid-state batteries have shown promising outcomes, new study attempts are now moving away from the growth of electrolytes and moving toward complete battery structural design and industrial production processes, with battery samples and prototypes constantly rolling off the assembly lines.

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Ionic conductivity of chalcogenide glasses

A. Pradel , M. Ribes , in Chalcogenide Glasses, 2014

7.7.1 Batteries

The development of solid state batteries which would help in overcoming the main problems of batteries containing liquid electrolytes, i.e. leakage and/or corrosion at the electrodes, required the use of solid electrolytes with high ionic conductivity in order to limit the ohmic drop at the electrodes. In this sense, lithium conducting chalcogenide glasses were excellent candidates with conductivity 10–100 times larger than that of their oxide counterparts. Several solid state batteries comprising lithium conducting chalcogenide glass or glass-ceramic as the solid electrolyte have been developed. ³⁸ ^, ⁴⁴ ^, ⁹⁷ ^, ^160–172 Thin film technology was also considered to develop rechargeable miniaturised Li batteries with Li⁺ conducting amorphous chalcogenide films as the electrolyte. ^47–49 ^, ¹⁶³

This work is described in more detail in Chapter 19.

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Chalcogenide glasses as electrolytes for batteries

M. Tatsumisago , A. Hayashi , in Chalcogenide Glasses, 2014

19.4.1 Fabrication of bulk-type all-solid-state batteries

A bulk-type solid-state battery composed of compressed electrode and electrolyte powders has been studied. Compared to a thin film battery, a bulk-type battery attracts much attention because the battery is suitable for large-sized energy-storage devices. Li₂S-based sulfide materials with high Li⁺ ion conductivity are promising solid electrolytes for bulk-type solid-state batteries. The electrochemical performance of solid-state In/LiCoO₂ cells with the Li₂S-SiS₂-Li₃PO₄ oxysulfide glasses was reported in 1994 (Aotani et al., 1994) and these cells with sulfide electrolytes have subsequently been developed.

In a cell with a liquid electrolyte, a favorable electrode–electrolyte interface is easily formed just by soaking electrodes in a liquid electrolyte, while in a cell with a solid electrolyte, electrode and electrolyte powders should be properly mixed to form intimate contact at the solid–solid interface. A composite electrode composed of an active material, a solid electrolyte, and a conductive additive is commonly used as a working electrode in bulk-type solid-state cells, in order to form continuous lithium ion and electron conducting paths to active material particles.

A schematic diagram of a typical all-solid-state electrochemical cell In/LiCoO₂ is shown in Fig. 19.9. The cell consists of a three-layered pellet prepared by uniaxial pressing at room temperature. The first layer is an indium foil as a negative electrode. The second layer is the 80Li₂S·20P₂S₅ glass-ceramic powder as a solid electrolyte (SE). The third layer is a composite powder as a positive electrode. In order to achieve smooth electrochemical reaction in the cell, the composite positive electrode composed of three kinds of powders was used: the active material (LiCoO₂), the SE powder providing lithium ion conduction path, and the conductive additive (acetylene black, AB) providing electron conduction paths. A cross-sectional SEM image of the three-layered pellet in the cell and schematic of the positive composite electrode are shown in Fig. 19.10. The composite positive electrode consisting of LiCoO₂, SE, and AB powders with a weight ratio of 20:30:3 was used for all-solid-state cells. Obvious grain-boundary in the composite electrode and solid electrolyte was not observed and intimate contacts between electrode and electrolyte were achieved by uniaxial cold-press. A typical thickness of positive electrode and solid electrolyte layers were ~ 70 μm and ~ 550 μm, respectively.

A typical charge–discharge performance of bulk-type solid-state cells with the 80Li₂S·20P₂S₅ glass-ceramic electrolyte is shown in Fig. 19.11 (Tatsumisago and Hayashi, 2008). LiCoO₂ and Li_4/3Ti_5/3O₄ were used as active materials. Both the cells operated as a secondary battery at 25 °C under a limited current density of 0.064 mA cm⁻² and kept a charge–discharge efficiency of 100% for several hundred cycles. The bulk-type solid-state cell exhibited an excellent cycle performance without capacity loss at room temperature.

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Catalysis, Green Chemistry and Sustainable Energy

Yihan Zhen , Yongdan Li , in Studies in Surface Science and Catalysis, 2020

6.2 Electrodes

Different from the electrodes of solid-state batteries, the electrodes of RFB provide just the location for redox reactions, and do not directly participate in the electrochemical reaction themselves. The active materials receive or lose electrons on the surface of the electrode to complete the electrochemical reactions. The ideal electrodes for RFBs should possess the following features: high reactivity and reversibility to the electrode reaction, high specific surface area and suitable porosity, high electrical conductivity, good chemical and mechanical stability, and low cost. According to the flow mode of the electrolyte on the electrode, the electrodes of RFBs can be categorized into "flow-through" and "flow-by" types. The former includes electrode materials with large pores, such as graphite felt, carbon felt, and metal foam, which are also referred to 3D electrodes. The latter includes electrode materials with small pores, such as carbon paper, carbon cloth, and black carbon, also known as 2D electrodes. Fig. 20.14 shows the schematics of flow mode of 2D and 3D electrodes [130]. Compared with the 2D electrode, the 3D electrode has larger pores and will not generate a large pressure drop when the liquid flows. In addition, it has higher specific surface area and can provide more reaction sites, which can improve the reaction rate and reduce the electrochemical polarization of the battery.

Generally, 3D carbon-based materials are used as electrodes for RFBs. However, pristine electrode materials are generally insufficient to acquire high electrochemical activity. Accordingly, many works are devoted to improving the catalytic activity and electrochemical activity by thermal, chemical, electrochemical, and bulk phase treatments, i.e., metal doping [42]. At this writing, the modification of flow battery electrodes is mainly focused on the VRFB systems [131–135]. The primary purpose of electrode optimization is to ensure long-term durability. By heat treatment at 400°C for 30 h, the performance of graphite felt was improved in terms of higher EE due to the enhanced hydrophilicity and increased active sites of C–O–H and C=O groups on the graphite felt [131].

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PRIMARY BATTERIES – NONAQUEOUS SYSTEMS | Solid-State: Silver–Iodine

B.B. Owens , ... P. Reale , in Encyclopedia of Electrochemical Power Sources, 2009

LiI(Al₂O₃) Dispersed-Phase Solid Electrolyte Battery

In 1965, the development of solid-state batteries was hindered by the lack of conductive ionic solids. As mentioned earlier, the four approaches led to promise in the area of reducing the internal resistance of the battery. A number of investigators focused on developing higher energy solid-state batteries that were not restricted to the use of silver as the anode material.

Initially, lithium iodide in pellet form was used as electrolyte in this type of pellet cell. However, the ionic conductivity of only 10⁻⁷ S cm⁻¹ at 25 °C severely limited the current and power capability of the batteries. It was then discovered that it is possible to increase the conductivity by the addition of up to 50 mol% high surface area alumina as a dispersion in the lithium iodide. Conductivity values of up to 10⁻⁴ S cm⁻¹ at 25 °C were reported.

A lithium negative electrode was coupled with a number of different solid cathodes to yield cells with voltages from 1.8 V to about 2.5 V for cell reactions such as

[XII] $2 Li + {PbI}_{2} \to LiI + Pb$

and

[XIII] $2 Li + {TiS}_{2} \to {Li}_{x} {TiS}_{2}$

Table 5 summarizes some of the systems investigated.

Table 5. Li/LiI(Al₂O₃)/metal salt cathode with dispersed-phase solid electrolyte of LiI–40 mol% Al₂O₃

Cathode	Cell voltage	Practical energy density Wh cm⁻³
PbI₂, Pb	1.9	0.1–0.2
PbI₂, PbS, Pb	1.9,1.8	0.3–0.6
TiS₂, S	2.5, 1.9	0.9–1

As reviewed by Shahi K, Wagner JB, and Owens BB (1983) Solid electrolyte lithium cells. In: Gabano JP (ed.) Lithium Batteries, ch. 15. London: Academic Press, Inc.; Owens BB, Skarstad PM, Untereker DF, and Passerini S (2001) In: Linden D and Reddy TB (eds.) Handbook of Batteries, 3rd edn., p. 15.1. New York: McGraw-Hill Book Company.

The schematic of a typical solid electrolyte cell with the dispersed-phase lithium iodide electrolyte is shown in Figure 7. These battery designs were very similar to those developed for the high-conductivity silver electrolytes and shown in Figures 1 and 3. Lithium is a soft metal that generally adhered well to the electrolyte pellet. However, in order to improve electrolyte–cathode pellet adhesion, the cathode typically contained a large volume fraction of the solid electrolyte.

Commercial batteries are no longer available. However, these batteries did demonstrate a reproducible level of performance over a wide range of temperature, from −40 up to 170 °C. Further description of these batteries can be found in earlier reviews of solid electrolyte batteries.

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MRI Studies of Plastic Crystals

K. Romanenko , in Annual Reports on NMR Spectroscopy, 2017

4.2 Temperature-Enhanced Conductivity

Translational ion mobility sufficient for practical solid-state battery applications should approach that of a liquid electrolyte. Indeed, NMR spectra of many OIPCs exhibited narrow lines indicative of high mobility similar to that observed in the liquid state [17,18,69,78–83].

NMR lineshapes of P₁₄₄₄FSI, P₁₂₂₂FSI, and P₁₂₂₄PF₆ were examined in the temperature range [18]. The liquid-like components (Δν _1/2 ≈ 1 kHz) were shown to exist even in low-temperature phases of the OIPCs but were easy to overlook due to low intensity (e.g., < 1% of total NMR signal) at the practical temperature range.

A narrow ¹H NMR signal was observed in all solid phases of P₁₄₄₄FSI (Fig. 18). Its intensity was highly sensitive to temperature and varied by several orders of magnitude (Fig. 26A ). Apparently, the increase in mobile phase with temperature occurred at expense of crystalline phase. This process was interpreted as "melting" of the crystallites at the interface region.

NMR diffusometry experiments supported the conclusion that the mobile region exists as a continuous phase distinct from the crystallites. The diffusion coefficient rapidly decreased with Δ asymptotically approaching constant values for longer observation times (Fig. 27A ). These patterns of restricted diffusion were seen in all three OIPC phases. The compartment size sampled by the cations over a 10-ms period was less than 300 nm at 280 K. Fig. 27B shows a gradual increase in ADC with temperature. This result indicated that there was no discontinuity in translational dynamics related to phase transitions.

As described in the previous chapter, ionic transport in OIPCs can be conceptualized using an analogy with flow in porous media. Permeability (k ₀) describes the capacity of porous media to conduct flow and is a fine analog of ionic conductivity (σ) [39,84]. Darcy's law introduced permeability as a coefficient between fluid flux and pressure gradient, the counterparts of current density and electric field, respectively. In sedimentary rocks, k ₀ is a complex function of porosity (Ɵ), grain morphology, and packing and can be anisotropic due to formation of bedding planes [85,86]. Homogeneous rock samples exhibited empirical power-law relationships between permeability and porosity [87]. Phenomenological proximity of ionic transport and fluid flow suggested that similar empirical models could be used for σ(f _m), where f _m should be considered as a measure of OIPC "porosity." A power-law form $σ = α f_{m}^{β}$ was used to quantify correlations between σ and f _m. Fig. 26B displays conductivity, log{σ(T)}, and power-law function of mobile fraction, log{αf _m ^β(T)}. The least square fit parameters were α = 0.0059 S cm^{− 1} and β = 2.32. Note, within a capillary tube model permeability scales as porosity squared [88].

In phase I of P₁₂₂₂FSI, the conductivity was approximated by $σ = 3 \times 10^{- 5} f_{m}^{0.88}$ (Fig. 28A ). The coefficient α was found to vary by an order of magnitude depending on cooling rate, while β values were similar. In P₁₂₂₄PF₆, the parameters α and β were phase dependent: $σ \approx 3 f_{m}^{3}$ in phase IV; $σ \approx 0.11 f_{m}^{2}$ in phase III; and σ ≈ (24.7f _m)¹⁶ in phase II (Fig. 28B). The dependence σ(f _m) was rather strong in phase II: a 10% increase in mobile fraction results in an order of magnitude increase in conductivity.

Phenomenological relationships between σ and f _m require further examination. With the possibility to be a general feature of OIPCs, these correlations can provide an approach for controlling conductivity through design of an interconnected conduction pathway.

In conclusion, strong temperature dependence of ionic conductivity commonly observed in neat OIPCs is largely associated with melting of crystal grains upon heating, leading to wider grain boundaries. This process results in the increased amount of mobile ions as well as in the increased capacity for ion transfer.

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Ceramics for electrochemical storage

Yulia Arinicheva , ... Valérie Pralong , in Advanced Ceramics for Energy Conversion and Storage, 2020

Solid electrolytes

One of the key components enabling rechargeable ASSB technology is a solid electrolyte. Solid electrolytes as described in detail in Section 4 should satisfy such technological requirements as high ionic conductivity in combination with negligible electronic conductivity, wide voltage window, chemical compatibility with cathode and anode materials, as well as relatively simple fabrication on a large scale with low cost (Manthiram et al., 2017). Generally, solid lithium- or sodium-ion conductors have been divided into three classes, which can complement each other to satisfy these requirements: (1) inorganic glassy or ceramic compounds; (2) organic polymers, and (3) composite or hybrid electrolytes consisting of a combination of the first two classes of materials (Manthiram et al., 2017; Hou et al., 2018a; Zheng et al., 2018).

Ionic transport in solid inorganic electrolytes is determined by the concentrations of mobile ions and vacancies, relative sizes of connected conduction pathways in crystal structures with Schottky and Frenkel point defects as well as by ion diffusion properties at the grain boundaries (Hou et al., 2018a,b; Zheng et al., 2018). Promising solid inorganic Li-ion electrolytes comprise amorphous lithium phosphorous oxynitride (LiPON) and with room-temperature conductivities up to several mS cm^{− 1} lithium-sulfide-based glass ceramics, NASICON-type phosphate [Li_{1 + x}Al_xTi_{2 − x}(PO₄)₃ (LATP)] and garnet-type oxide [Li₇La₃Zr₂O₁₂ (LLZO)] ceramic electrolytes. Typical solid inorganic electrolytes for Na(-ion) ASSBs, also possessing relatively high room-temperature ionic conductivities over 1 mS cm^{− 1}, include Na-β″-alumina, Na superionic conductors [NASICON, i.e., Na_3.1Zr_1.95Mg_0.05Si₂PO₁₂ (Song et al., 2016)], sulfides (i.e., Na₃PS_4, Na_10.8Sn_1.9PS_11.8), and complex hydrides (e.g., sodium borohydride) (Yu et al., 2018b; Hou et al., 2018a,b).

Solid polymer electrolytes have generally significantly lower ionic conductivity than ceramic electrolytes but show mechanical flexibility, light weight, convenience of fabrication process, and accommodation of volume changes of electrodes during charge/discharge. In solid polymer electrolytes, Li- or Na salts are solvated by polymer chains in, for example, polyethylene oxide (PEO)- or polysiloxane-based polymers and Li or Na ions move through the connected polymer chains. The ionic conductivity of a solid polymer electrolyte is related to the number of mobile ions and the segmental motions of the polymer chains. The ionic transport in the connected polymer chains can be blocked by crystalline chain segments, which form below the glass transition temperature (T _g). T _g can be lowered, for example, by adding nanosized fillers. However, a relatively low ionic conductivity at room temperature still represents the major drawback of polymer electrolytes (Zheng et al., 2018; Hou et al., 2018a,b).

Composite or hybrid electrolytes, combining the advantages of (glass-)ceramic and polymer ionic conductors, provide improved ionic conductivity with high flexibility for reducing the interfacial resistances between solid electrolytes and electrodes (Zheng et al., 2018; Hou et al., 2018a,b).

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What Is a Solid State Battery Made of

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What Is a Solid State Battery Made of

Solid State Battery

SECONDARY BATTERIES – LITHIUM RECHARGEABLE SYSTEMS | Electrolytes: Solid Sulfide

Composite interface – Graphite/SE interface

Electrodes

13.3.1 Nanosized transition-metal oxides as negative electrode materials for lithium ion batteries