A solid-state battery is a battery technology that uses solid electrodes and a solid electrolyte, instead of the liquid or polymer gel electrolytes found in lithium-ion or lithium polymer batteries.
While solid electrolytes were first discovered in the 19th century, several drawbacks, such as low energy densities, have prevented widespread application. Developments in the late 20th and early 21st century have caused renewed interest in solid-state battery technologies, especially in the context of electric vehicles, starting in the 2010s.
Solid-state batteries can provide potential solutions for many problems of liquid Li-ion battery, such as flammability, limited voltage, unstable solid-electrolyte interphase formation, poor cycling performance and strength.
Materials proposed for use as solid electrolytes in solid-state batteries include ceramics (e.g., oxides, sulfides, phosphates), and solid polymers. Solid-state batteries have found use in pacemakers, RFID and wearable devices. They are potentially safer, with higher energy densities, but at a much higher cost. Challenges to widespread adoption include energy and power density, durability, material costs, sensitivity and stability.
By the late 1950s, several electrochemical systems employed solid electrolytes. They used a silver ion, but had some undesirable qualities, including low energy density and cell voltages, and high internal resistance. A new class of solid-state electrolyte, developed by the Oak Ridge National Laboratory, emerged in the 1990s, which was then used to make thin film lithium-ion batteries.
As technology advanced into the new millennium, researchers and companies operating in the automotive and transportation industries experienced revitalized interest in solid-state battery technologies. In 2011, Bolloré launched a fleet of their BlueCar model cars, first in cooperation with carsharing service Autolib, and later released to retail customers. The car was meant to showcase the company's diversity of electric-powered cells in application, and featured a 30 kWh lithium metal polymer (LMP) battery with a polymeric electrolyte, created by dissolving lithium salt in a co-polymer (polyoxyethylene).
In 2012, Toyota soon followed suit and began conducting experimental research into solid-state batteries for applications in the automotive industry in order to remain competitive in the EV market. At the same time, Volkswagen began partnering with small technology companies specializing in the technology.
A series of technological breakthroughs ensued. In 2013, researchers at the University of Colorado Boulder announced the development of a solid-state lithium battery, with a solid composite cathode based on an iron-sulfur chemistry, that promised higher energy capacity compared to already-existing SSBs.
In 2017, John Goodenough, the co-inventor of Li-ion batteries, unveiled a solid-state battery, using a glass electrolyte and an alkali-metal anode consisting of lithium, sodium or potassium. Later that year, Toyota announced the deepening of its decades-long partnership with Panasonic, including a collaboration on solid-state batteries. Due to its early intensive research and coordinated collaborations with other industry leaders, Toyota holds the most SSB-related patents. However, other car makers independently developing solid-state battery technologies quickly joined a growing list that includes BMW, Honda, Hyundai Motor Company and Nissan. Other automotive-related companies, such as Spark plug maker NGK, have retrofitted their business expertise and models to cater to evolving demand for ceramic-based solid state batteries, in the face of perceived obsolescence of the conventional fossil-fuel paradigm.
Major developments continued to unfold into 2018, when Solid Power, spun off from the University of Colorado Boulder research team, received $20 million in funding from Samsung and Hyundai to establish a small manufacturing line that could produce copies of its all-solid-state, rechargeable lithium-metal battery prototype, with a predicted 10 megawatt hours of capacity per year. Solid Power anticipates "entering the formal automotive qualification process" in early 2022.
QuantumScape, another solid-state battery startup that spun out of a collegiate research group (in this case, Stanford University) drew attention that same year, when Volkswagen announced a $100 million investment into the team's research, becoming the largest stakeholder, joined by investor Bill Gates. With the goal to establish a joint production project for mass production of solid-state batteries, Volkswagen endowed QuantumScape with an additional $200 million in June 2020, and QuantumScape IPO'd on the NYSE on November 29, 2020, as part of a merger with Kensington Capital Acquisition, to raise additional equity capital for the project. QuantumScape has "scheduled mass production to begin in the second half of 2024".
Qing Tao started the first Chinese production line of solid-state batteries in 2018 as well, with the initial intention of supplying SSBs for “special equipment and high-end digital products”; however, the company has spoken with several car manufacturers with the intent to potentially expand into the automotive space.
In July 2021, Murata Manufacturing announced that it will begin mass production of all-solid-state batteries in the coming months, aiming to supply them to manufacturers of earphones and other wearables. The battery capacity is up to 25mAh at 3.8v, making it suitable for small mobile devices such as earbuds, but not for electric vehicles. Lithium Ion cells used in electric vehicles typically offer 2,000 to 5,000 mAh at similar voltage: an EV would need at least 100 times as many of the Murata cells to provide equivalent power.
In September 2021, Toyota announced their plan to use a solid state battery in some future car models. In addition, in the field of research, pure silicon μSi||SSE||NCM811 solid state battery was assembled by Darren H.S Tan et al. using μSi electrode (purity of 99.9 wt %), solid state electrode (SSE) and lithium nickel cobalt manganese oxide (NCM811). This kind of solid state battery has a high current density up to 5 mA cm−2, possesses a wide range of working temperature (-20 °C and 80 °C), and areal capacity up to 11 mAh cm−2 (2890 mAh/g). At the same time, after 500 cycles under 5 mA cm−2, the batteries still provide 80% of capacity retention, which is the best performance of μSi all solid-state battery reported so far.
Solid-state electrolytes (SSEs) candidate materials include ceramics such as lithium orthosilicate, glass, sulfides and RbAg4I5. Mainstream oxide solid electrolytes include Li1.5Al0.5Ge1.5(PO4)3 (LAGP), Li1.4Al0.4Ti1.6(PO4)3 (LATP), perovskite-type Li3xLa2/3-xTiO3 (LLTO), and garnet-type Li6.4La3Zr1.4Ta0.6O12 (LLZO) with metallic Li. The thermal stability versus Li of the four SEs was in order of LAGP < LATP < LLTO < LLZO. Chloride superionic conductors have been proposed as another promising solid electrolyte. They are ionic conductive as well as deformable sulfides, but at the same time not troubled by the poor oxidation stability of sulfides. Other than that, their cost is considered lower than oxide and sulfide SSEs. The present chloride solid electrolyte systems can be divided into two types: Li3MCl6  and Li2M2/3Cl4. M Elements include Y, Tb-Lu, Sc, and In. The cathodes are lithium based. Variants include LiCoO2, LiNi1/3Co1/3Mn1/3O2, LiMn2O4, and LiNi0.8Co0.15Al0.05O2. The anodes vary more and are affected by the type of electrolyte. Examples include In, GexSi1−x, SnO–B2O3, SnS –P2S5, Li2FeS2, FeS, NiP2, and Li2SiS3.
One promising cathode material is Li-S, which (as part of a solid lithium anode/Li2S cell) has a theoretical specific capacity of 1670 mAh g−1, "ten times larger than the effective value of LiCoO2". Sulfur makes an unsuitable cathode in liquid electrolyte applications because it is soluble in most liquid electrolytes, dramatically decreasing the battery's lifetime. Sulfur is studied in solid state applications. Recently, a ceramic textile was developed that showed promise in a Li-S solid state battery. This textile facilitated ion transmission while also handling sulfur loading, although it did not reach the projected energy density. The result "with a 500-μm-thick electrolyte support and 63% utilization of electrolyte area" was "71 Wh/kg." while the projected energy density was 500 Wh/kg.
A Li/LiFePO4 battery shows promise as a solid state application for electric vehicles. A 2010 study presented this material as a safe alternative to rechargeable batteries for EV's that "surpass the USABC-DOE targets".
Hybrid and plug-in electric cars use a variety of battery technologies, including li-ion, nickel–metal hydride (NiMH), lead–acid, and electric double-layer capacitor (or ultracapacitor), with li-ion dominating the market. In August 2020, Toyota started road testing of their prototype vehicle, LQ Concept, equipped with a solid-state battery. In September 2021, Toyota unveiled its strategy on battery development and supply, in which solid-state battery is to be adopted first in their hybrid electric vehicles to utilize its characteristics.
The characteristics of high energy density and keeping high performance even in harsh environments are expected in realization of new wearable devices that are smaller and more reliable than ever.
Equipment in space station
In March 2021, an industrial manufacturer Hitachi Zosen Corporation has developed a solid-state battery, claiming to have one of the highest capacities in the industry, and explained about its usage in harsh conditions in space environment. They have already made agreement with the Japan Aerospace Exploration Agency (JAXA) to test their solid-state batteries in space, and the battery will power camera equipment in Japan's Experiment Module Kibō on the International Space Station (ISS).
Solid-state batteries are traditionally expensive to make and employ manufacturing processes thought to be difficult to scale, requiring expensive vacuum deposition equipment. As a result, costs become prohibitive in consumer-based applications. It was estimated in 2012 that, based on then-current technology, a 20 Ah solid-state battery cell would cost US$100,000, and a high-range electric car would require between 800 and 1,000 of such cells. Likewise, cost has impeded the adoption of solid-state batteries in other areas, such as smartphones.
Temperature and pressure sensitivity
High interfacial resistance between a cathode and solid electrolyte has been a long-standing problem for all-solid-state batteries.
The interfacial instability of the electrode-electrolyte has always been a serious problem in solid state batteries. After solid state electrolyte contacts with electrode, the chemical and/or electrochemical side reactions at the interface usually produce a passivated interface, which impedes the diffusion of Li+ across the electrode-SSE interface. Upon high-voltage cycling, some SSEs may undergo oxidative degradation.
Solid lithium (Li) metal anodes in solid-state batteries are replacement candidates in lithium-ion batteries for higher energy densities, safety, and faster recharging times. Such anodes tend to suffer from the formation and the growth of Li dendrites.
Dendrites penetrate the separator between the anode and the cathode causing short circuits. This causes overheating, which may result in fires or explosions from thermal runaway. Li dendrites reduce coulombic efficiency.
Dendrites commonly form during electrodeposition during charge and discharge. Li ions combine with electrons at the anode surface as the battery charges - forming a layer of lithium metal. Ideally, the lithium deposition occurs evenly on the anode. However, if the growth is uneven, dendrites form. The component of Li dendrites was confirmed as LixCy, Li2O, and LixCyOz in 2018.
Stable solid electrolyte interphase (SEI) was found to be the most effective strategy for inhibiting dendrite growth and increasing cycling performance. Solid-state electrolytes (SSEs) may prevent dendrite growth, although this remains speculative. A 2018 study identified nanoporous ceramic separators that block Li dendrite growth up to critical current densities.
They may avoid the use of dangerous or toxic materials found in commercial batteries, such as organic electrolytes.
Because most liquid electrolytes are flammable and solid electrolytes are nonflammable, solid-state batteries are believed to have lower risk of catching fire. Fewer safety systems are needed, further increasing energy density. Recent studies show that heat generation inside is only ~20-30% of conventional batteries with liquid electrolyte under thermal runaway.
Thin film solid state batteries
The earliest thin film solid state batteries is found by Keiichi Kanehori in 1986, which is based on the Li electrolyte. However, at that time, the technology was insufficient to power larger electronic devices so it was not fully developed. During recent years, there has been much research in the field. Garbayo demonstrated that “polyamorphism” exists besides crystalline states for thin film Li-garnet solid state batteries in 2018, Moran demonstrated that ample can manufacture ceramic films with the desired size range of 1–20 μm in 2021.
Anode materials: Li is favored because of its storage properties, alloys of Al, Si and Sn are suitable for anode, too.
Cathode materials: require having light weight, good cyclical capacity and high energy density. Usually include LiCoO2, LiFePO4, TiS2, V2O5and LiMnO2.
Some methods are listed below.
- Physical methods:
- Magnetron sputtering (MS) is one of the most widely used processes for thin film manufacturing, which is based on physical vapor deposition.
- Ion-beam deposition (IBD) is similar to the first method, however, bias is not applied and plasma doesn’t occur between the target and the substrate in this process.
- Pulsed laser deposition (PLD), laser used in this method has a high power pulses up to about 108 W cm−2.
- Vacuum evaporation (VE) is a method to prepare alpha-Si thin films. During this process, Si evaporates and deposits on a metallic substrate.
- Chemical methods:
- Electrodeposition (ED) is for manufacturing Si films, which is convenient and economically viable technique.
- Chemical vapor deposition (CVD) is a deposition technique allowing to make thin films with a high quality and purity.
- Glow discharge plasma deposition (GDPD) is a mixed physicochemical process. In this process, synthesis temperature has been increased to decrease the extra hydrogen content in the films.
Development of thin film system
- Lithium-Oxygen and Nitrogen based polymer thin film electrolytes has got fully used in solid state batteries.
- Non-Li based thin film solid state batteries have been studied, such as Ag-doped germanium chalcogenide thin film solid state electrolyte system. Barium-doped thin film system has also been studied, which thickness can be 2μm at least. In addition, Ni can also be a component in thin film.
- There are also other methods to fabricate the electrolytes for thin film solid state batteries, which are 1.electrostatic-spray deposition technique, 2. DSM-Soulfill process and 3. Using MoO3 nanobelts to improve the performance of lithium based thin film solid state batteries.
- Compared with other batteries, the thin film batteries have both high gravimetric energy density and volumetric energy density, these are important indicators to measure battery performance of energy stored.
- In addition to high energy density, thin-film solid-state batteries have long lifetime, outstanding flexibility and low weight. These properties make thin film solid state batteries get widely used in various fields such as low carbon vehicles, military facilities and medical devices.
- Its performance and efficiency are constrained by the nature of its geometry. The current drawn from a thin film battery largely depends on the geometry and interface contacts of the electrolyte/cathode and the electrolyte/anode interfaces
- Low thickness of the electrolyte and the interfacial resistance at the electrode and electrolyte interface affect the output and integration of thin film systems.
- During the charging-discharging process, considerable change of volumetric makes the loss of material.
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