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Solid electrolytes do not automatically stop lithium dendrites. In lithium–LLZO–lithium cells, researchers have observed both uneven lithium plating at electrode interfaces and lithium-ion reduction along grain boundaries as routes to dendrite formation. Which route matters—and whether it leads to penetration or an internal short—depends on the electrolyte’s structure, its interfaces and the cell’s operating conditions.
How do lithium dendrites form in solid-state batteries?
A dendrite is a lithium-rich growth that can extend into an electrolyte. Replacing a liquid electrolyte with a solid one changes the environment in which lithium moves; it does not make lithium deposition or penetration impossible. Recent LLZO studies point to multiple pathways rather than one universal explanation.
Uneven plating at an interface
During charging, lithium can plate nonuniformly at the electrode–electrolyte interface. In a 2025 study of Li/LLZO/Li cells, Liu and colleagues used tracer-exchange solid-state NMR and in-situ MRI to investigate dendrite formation. They associated an early, rapid growth phase with uneven interfacial plating.
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The same study identified a second route: local reduction of Li+ at LLZO grain boundaries. MRI showed a period in which growth stalled between the rapid plating-associated phase and later, slower bulk nucleation attributed to lithium-ion reduction. The sequence suggests that more than one process can contribute over the course of a cell’s behavior.
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The authors also discuss amorphous dendrite formation followed by crystallization, defect chemistry in the solid electrolyte and operating conditions as relevant to how these processes interact. These findings are specific to the tested LLZO cell system; they do not establish that every solid electrolyte forms dendrites by the same routes.
Cracks and grain-boundary structure
Grain boundaries are not all alike. A 2025 LLZO study by You and colleagues found that crack-like voids at boundaries can facilitate lithium protrusions. The study’s analysis and simulations link these voids with a route for lithium growth into the electrolyte, rather than treating the solid material as a uniformly intact barrier.
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Why can dendrites cause durability problems?
If lithium penetrates a solid electrolyte, it can create a path through the separator and cause an internal short circuit. That is a potential failure route, not a statement that every dendrite immediately shorts a cell. The extent and timing of damage depend on the material, its defects and interfaces, and how the cell is operated.
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Durability is therefore not determined by whether an electrolyte is labelled “solid” alone. Interface uniformity, grain-boundary structure, cracks or voids, electronic conduction, mechanical stress and space-charge effects are among the interacting factors discussed in a 2024 review by Yang and colleagues. A 2026 review by Weckelmann and colleagues gives particular attention to low lithium self-diffusion coupled with interfacial inhomogeneities. That broader framing helps identify factors to investigate, but it does not replace chemistry-specific experimental evidence.
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What approaches are researchers investigating?
Proposed mitigations target different parts of the problem. The 2024 review surveys several approaches; these are research strategies, not demonstrated fixes for commercial cycle life across solid-state batteries.
| Approach | Pathway or feature targeted | What the cited work establishes |
|---|---|---|
| Electrolyte composition and design | Electrolyte properties and defect-related pathways | Discussed as a mitigation strategy in Yang et al.’s 2024 review; the review does not establish one composition as a universal solution. |
| Electron-blocking interface buffer layers | Electronic transport and interfacial behavior | Discussed as a strategy in Yang et al.’s 2024 review; a broadly applicable durability benefit is not established there. |
| Surface or current-collector modification | Interface conditions and lithium deposition | Surveyed in Yang et al.’s 2024 review as approaches researchers have proposed or investigated. |
| Added physical fields | Conditions that influence lithium growth | Included among the strategies surveyed by Yang et al.’s 2024 review; the review does not establish a general commercial solution. |
| Selective grain-boundary amorphization | LLZO grain-boundary structure and lithium aggregation | You et al.’s 2025 LLZO study reported suppressed lithium aggregation and protrusions, alongside improved interfacial electronic and mechanical properties and a slight reduction in ionic conductivity. |
The grain-boundary result illustrates a practical trade-off: changing microstructure may reduce a growth pathway while also affecting ion transport. Its reported outcome is tied to LLZO and the study’s conditions, not a guarantee for other chemistries or cell designs.
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What the evidence does—and does not—show
The strongest direct evidence in these studies concerns LLZO garnet cells: the 2025 MRI and NMR work resolves two formation routes and their observed sequence, while the 2025 grain-boundary study examines voids and amorphization. The 2024 and 2026 reviews synthesize broader proposed mechanisms and approaches; review-level coverage should not be mistaken for direct experimental confirmation of each mechanism in every electrolyte.
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- Multiple mechanisms can operate in one LLZO cell, so a single-mechanism explanation may miss later behavior.
- Microstructure and interfaces matter: a solid electrolyte can contain boundary voids or other nonuniformities.
- Mitigation evidence must be read with its chemistry, test conditions and trade-offs in view.
- Laboratory suppression of protrusions does not by itself establish commercial battery cycle life.
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