Author: Iñigo Careaga, strategy & communication manager, CIC energiGUNE

Lithium and sodium are neighbours in the periodic table. Both are alkali metals, both have a single electron in their outer shell, and both can be used to shuttle ions between two electrodes to store and release electrical energy. At first sight, replacing lithium with sodium in a rechargeable battery might therefore seem straightforward.

There are good reasons to try. Sodium is widely available and sodium-ion batteries can rely on electrode materials containing abundant elements such as iron and manganese. But chemical similarity does not mean electrochemical equivalence. A sodium ion is larger and heavier than a lithium ion, and its interaction with the materials surrounding it is different. As a consequence, replacing Li⁺ with Na⁺ changes much more than the identity of the charge carrier.

The electrodes have to accommodate a different ion. Their structures may respond differently as sodium is inserted and removed. The electrolyte has to transport and solvate it. New interfaces form between the electrolyte and the electrodes. Even graphite, the standard anode material of most commercial lithium-ion batteries, does not store sodium under conventional conditions nearly as effectively as it stores lithium ¹.

A sodium-ion battery is therefore not simply a lithium-ion battery containing a different element. Understanding why requires looking at what happens to sodium once it enters the battery.

Graphite does not play by the same rules

Charging a conventional lithium-ion battery involves moving lithium ions from the positive electrode through the electrolyte and storing them in the negative electrode. Graphite is particularly good at this job. Its carbon atoms are arranged in sheets, and lithium can reversibly occupy the spaces between them, a process known as intercalation. It would be convenient if sodium behaved in the same way. It largely does not.

The poor ability of conventional graphite to accommodate sodium has long been one of the reasons why lithium-ion concepts cannot simply be transferred to sodium-ion batteries. Instead, one of the most widely studied negative-electrode materials is hard carbon ².

Hard carbon is still carbon, but structurally it is very different from graphite. Rather than a regular stack of extended carbon sheets, it contains disordered graphitic domains, defects and pores. This disordered architecture provides environments in which sodium can be stored, but it also makes the underlying mechanism considerably harder to describe.

Where exactly does the sodium go? Researchers have proposed contributions from adsorption at defects and surfaces, insertion between graphitic layers and storage associated with nanopores. The relative importance of these mechanisms depends on the structure and microstructure of the carbon. This is more than a microscopic detail: where and how sodium is stored determines the voltage profile, reversible capacity, first-cycle losses and, ultimately, the energy that a complete cell can deliver.

Researchers at CIC energiGUNE and collaborators have studied this connection between charge-storage mechanisms, carbon structure and electrochemical performance ³. Their analysis highlights an important point: maximizing the amount of sodium that an anode can store is not enough. The potential at which that storage occurs and the irreversible losses during the first cycle are equally important when the material is incorporated into a full battery.

The problem is therefore not simply to find a carbon that accommodates more sodium. It is to understand how its structure stores sodium and then engineer that structure so that capacity, voltage and efficiency improve together. This has led researchers to explore different ways of controlling hard-carbon structure, including the use of lignocellulosic biomass as a precursor. Work has shown that even apparently simple processing decisions, such as acid treatment of the biomass precursor, can affect the resulting carbon and its behaviour as a sodium-ion anode ⁴.

And the negative electrode is only half of the problem. At the positive electrode, sodium ions have to repeatedly leave and re-enter a solid structure. Layered transition-metal oxides are attractive candidates because sodium can be reversibly extracted from and inserted into spaces between layers of metal and oxygen atoms. Compositions based on relatively abundant elements such as iron and manganese are particularly interesting ⁵.

Again, however, accommodating sodium is not enough. The host structure has to survive the process. A useful example is the layered oxide P2-Na₂/₃[Fe₁/₂Mn₁/₂]O₂, investigated by researchers from CIC energiGUNE and collaborators ⁶. The material can provide high capacity, but its long-term stability strongly depends on the voltage range over which it is operated.

This produces a familiar battery dilemma. Increasing the operating voltage can increase the amount of energy extracted from a material. But pushing the electrode further can also trigger structural transformations that make subsequent cycles less reversible.

The researchers compared cells operating in different voltage windows and combined electrochemical measurements with structural characterization and theoretical calculations. Above approximately 4.0 V versus Na+/Na, the cathode undergoes a high-voltage phase transition. Avoiding this transition improves capacity retention, revealing a direct connection between the structural state of the electrode and its long-term electrochemical behaviour.

Changing the chemical composition can also alter this structural response. In another study, researchers investigated the effect of introducing titanium into sodium manganese-rich layered oxides ⁷. A certain degree of Ti substitution helped the crystal structure accommodate electrochemically induced strain. Too little was insufficient to stabilize it, while further substitution introduced other destabilizing effects.

Other studies have approached the same problem from a different angle, examining how the precise stoichiometry of P2 layered oxides affects their performance ⁸, or following their structural evolution under different current rates and dopants using operando techniques ⁹. The lesson is that there is no single property called “a good sodium cathode”. Composition, atomic arrangement, voltage and cycling conditions are interconnected. Even an element that does not directly provide the stored charge can determine how well the electrode survives sodium repeatedly moving through its structure.

A different chemistry

Layered oxides are not the only possible positive electrodes. Sodium chemistry allows other structural families to be explored.

One particularly instructive example is NaFePO₄, the sodium analogue of the well-known lithium iron phosphate chemistry. Researchers involving CIC energiGUNE have used in situ X-ray diffraction to follow how NaFePO₄ changes during sodium insertion and extraction ¹⁰. They have also shown that the reaction mechanism itself depends on how rapidly the electrode is charged or discharged ¹¹.

This is a subtle but important point. We often describe an electrode material as if it had a fixed reaction mechanism. In practice, what happens inside it can depend on how the battery is operated. Computational work has gone further by investigating sodium diffusion in NaₓFePO₄ ¹². Combining experiments and modelling in this way makes it possible to connect what is observed at the battery level with the motion of ions through an atomic structure.

But even understanding both electrodes is not enough. Between them lies the electrolyte, and the sodium ion spends much of its journey there. It becomes surrounded by solvent molecules, travels across the cell and eventually reaches an electrode surface. At that interface the electrolyte can decompose, producing a solid-electrolyte interphase, or SEI.

This apparently thin layer can have a disproportionate influence on battery behaviour. Researchers at CIC energiGUNE have investigated both the composition and evolution of the SEI in sodium-ion electrodes ¹³ and, more broadly, the relationship between electrode-electrolyte interphases, transport properties and electrochemical performance in non-aqueous sodium-ion batteries ¹⁴.

The interface illustrates particularly well why changing lithium for sodium is not a simple substitution. The chemistry of the ion influences its solvation, its transport and the decomposition reactions that occur when it reaches an electrode. A material that can reversibly store sodium may still perform poorly if the interface around it continuously consumes electrolyte or sodium during cycling.

This is why sodium-ion research has to consider the cell as a system. Graphite may have to give way to hard carbon. Positive electrodes require structures able to tolerate repeated sodium insertion and extraction. Electrolytes and additives have to create suitable transport conditions and stable interfaces.

And every attempt to solve one of these problems can affect the others.

Sodium is not the new lithium

Lithium has a fundamental advantage that materials engineering cannot simply remove: it is the lightest metal and has a very low electrochemical potential. Sodium is heavier and its electrochemical potential is less favourable, placing intrinsic constraints on the gravimetric energy density that sodium-ion batteries can reach.

That does not necessarily make sodium a worse battery chemistry. Energy density is only one parameter of an electrochemical storage system. Cost, raw-material availability, lifetime, power, safety and operating temperature can become equally important depending on the application. A battery designed for a mobile phone, an electric vehicle or stationary storage does not necessarily have to optimize the same variables. And sodium chemistry itself offers several possible ways of balancing them.

CIC energiGUNE researchers have explored, for example, low-cost phosphate-based cathodes for aqueous sodium-ion batteries ¹⁵, Prussian Blue compounds as positive electrodes in aqueous systems ¹⁶, alternative sodium layered oxides [5,8,9], hard-carbon anodes [2,3,4] and even materials such as NaTiOPO₄ designed to modify or potentially avoid some of the interfacial problems normally associated with sodium-ion anodes ¹⁷.

These are not different routes towards exactly the same battery. They represent different ways of deciding which compromises are acceptable.

This changes the original question. The relevant challenge may not be how to make sodium behave as much like lithium as possible. Research on hard carbons shows that sodium may require a different type of host structure. Work on layered oxides shows that extracting more energy from an electrode can alter its structure and compromise its stability. Studies of NaFePO₄ show that the reaction pathway itself can depend on cycling conditions. And research on interfaces shows that storing sodium reversibly is only part of the problem: the chemistry taking place around the active material matters as well.

Sodium-ion batteries are therefore not lithium-ion batteries in which one element has simply been exchanged for another. Changing the ion changes the materials that host it, the structures they adopt, the reactions they undergo and the interfaces they form.

Sodium may not need to beat lithium at its own game. The more interesting question is whether understanding its different chemistry will allow us to play a different one.

 

The BRTA is a consortium that remains a step ahead of future socio-economic challenges worldwide and in the Basque Autonomous Community; it addresses them through research and technological development, thus projecting itself internationally. The BRTA centres collaborate to generate knowledge and transfer it to Basque society and industry so as to make them more innovative and competitive. The BRTA is an alliance of 17 R&D centres and cooperative research centres with the support of the Basque Government, the SPRI and the Chartered Provincial Councils of Araba, Bizkaia and Gipuzkoa.

 

The post Why can’t we simply replace lithium with sodium in batteries? appeared first on Mapping Ignorance.

 

Authors: Eider Fernandez & Igor Baroja-Careaga, Esneki Zentroa (Leartiker S.COOP)

 

Probiotics are part of a rapidly expanding field of research. They are live microorganisms that, when administered in adequate amounts, may confer health benefits[1]. Among the most extensively studied probiotics, some species of Lactobacillus and Bifidobacterium have been associated with the maintenance of gut microbiota balance and with several physiological functions[2]. Producing these microorganisms usually requires nutrient-rich culture media. But what if such bacteria could be obtained from a food by-product nowadays regarded as waste? This question formed the starting point of a study carried out by Esneki Dairy Centre – Leartiker to assess the potential of cheese whey as a substrate for producing microbial biomass enriched in microorganisms with probiotic potential.

The challenge of cheese whey

Cheesemaking inevitably generates substantial amounts of whey: a yellowish liquid released from the curd that still carries lactose, soluble proteins, minerals and other valuable compounds. In fact, whey can represent around 85% of the original milk volume used in cheese production[3].

Despite this nutritional richness, whey remains a difficult stream to manage for many artisanal dairies. This is particularly true in the Basque Country, where many cheesemaking farms are small, family-run businesses located in rural areas[4]. Its highly perishable nature means that whey must be preserved or processed soon after production, making storage, collection and transport especially challenging when volumes are small and geographically dispersed.

Moreover, uncontrolled whey discharge results in a high organic load that can affect aquatic ecosystems. Paradoxically, the same nutrients that make cheese whey a potential pollutant are also what give it considerable biotechnological value.

A natural culture medium

From a microbiological standpoint, cheese whey is not merely a residual stream, but a naturally nutrient-rich matrix[5]. Its lactose content, together with soluble proteins, minerals and other available compounds, provides a favourable environment for the growth of lactic acid bacteria, widely used microorganisms in fermented foods and increasingly explored for their probiotic potential.

The working hypothesis was simple: by steering whey fermentation under controlled conditions, it could be possible to recover a biomass enriched in microorganisms of interest, while at the same time increasing the stability and value of the by-product itself.

To explore this possibility, several fermentation strategies were tested using whey generated during the production of blue cheese from pasteurised cow’s milk. The study compared three different approaches:

• Fermentation of previously pasteurised whey (Protocol 1).
• Fermentation of whey after a deproteinisation step (Protocol 2).
• Direct fermentation of raw whey, without any prior treatment (Protocol 3).

Two different blends of commercial microorganisms, inspired by the naturally diverse microbial communities found in kefir, were also evaluated. These included; Choozit Kefir DV LYO 1000L (Danisco) (starter culture A) and Ferlac Kefir Type C (Abiasa) (starter culture B). Additionally, unfermented whey (that is, whey to which no starter cultures were added and which was not subjected to fermentation) from each protocol was analysed as a control sample. Controlled fermentation processes were carried out under monitored conditions. Throughout the fermentation, key parameters were monitored, including temperature (25 ± 1 °C), incubation time (16 ± 1 h for starter culture A and 21 ± 1 h for starter culture B) and pH evolution, with fermentation being considered complete once the pH fell below 4,6. These measurements allowed the identification of the conditions that most effectively supported the growth and enrichment of the target microbial populations.

 

Exploring the microbiome through metagenomics

However, assessing the success of a fermentation process requires more than simply determining how many microorganisms grow. It is also essential to identify which species are present and how the microbial community changes over time.

Traditional culture-based microbiological methods remain fundamental tools for quantifying and isolating viable microorganisms. Yet they have important limitations when complex microbial communities need to be characterised, as they only detect microorganisms able to grow under the selected culture conditions. As a result, part of the microbial diversity present in the sample may remain undetected. To obtain a more comprehensive view of the microbial community, the study incorporated high-throughput amplicon sequencing, an approach that enables the direct analysis of DNA present in a sample and the identification of microorganisms regardless of their ability to grow under laboratory conditions.

Bacterial communities were characterised by amplifying the V4 region of the 16S rRNA gene, one of the most widely used markers in bacterial diversity studies. Fungal and yeast communities were analysed through the ITS region — the Internal Transcribed Spacer — which is considered the standard marker for fungal diversity studies.

Sequencing was performed using Illumina technology, generating approximately 100,000 reads per sample for bacteria and around 40,000 reads for fungi and yeasts. These sequences were then compared against specialised databases to determine the identity of the microorganisms present and estimate their relative abundance.

Before interpreting the results, sequencing depth was assessed using rarefaction curves. These curves showed a clear trend towards saturation, indicating that most of the microbial diversity present in the samples had been adequately captured.

Which protocol worked best?

High-throughput amplicon sequencing revealed clear differences among the fermentation strategies tested.

Fermentations carried out using raw whey (Protocol 3) maintained a more diverse bacterial community than those in which the whey had first been subjected to thermal treatment (Protocol 1 and Protocol 2), as can be seen in Figure 1, as can be seen in Figure 1, the number of observed microbial taxa increases with sequencing depth. This suggests that the partial preservation of the native microbiota originating from the cheesemaking process may play an important role in shaping the fermentation outcome.

 

 

 

In contrast, the diversity of moulds and yeasts decreased. This trend may be related to the origin of the whey, which was obtained from blue cheese production, where specific mould (Penicillium roquefoti) species are deliberately enriched during manufacture. The competitive advantage of these dominant fungi appears to favour the development of a more specialised microbial community, reducing the abundance and diversity of other microbial populations present in the whey (Figure 2).

 

 

Principal coordinates analysis (PCoA) based on Jaccard distances (Figure 3) showed a clear separation among the different fermentation protocols, indicating that each strategy gave rise to distinct microbial communities. In parallel, the relative abundance of profiles (Figure 4) made it possible to visualise how particular species increased or decreased depending on the conditions applied.

 

 

 

 

Amplicon sequencing also enabled the identification of the dominant microorganisms during the process. In most samples, Lactococcus lactis was particularly abundant. This result was expected, as this bacterium was included in the commercial starts cultures used and is widely employed in dairy fermentations. However, some fermentation conditions, particularly those involving starter culture B, also favoured the development of species such as Lacticaseibacillus rhamnosus and Bifidobacterium animalis, wich were also present in the commercial starter culture. These microorganisms are frequently associated with probiotic applications[6]^,[7]^,[8].

To identify the most suitable protocol for producing a fermented whey enriched in microorganisms with probiotic potential, both microbial abundance (including aerobic mesophilic bacteria, yeasts and moulds) and the diversity of the resulting microbial communities were evaluated. The highest microbial counts were obtained in whey samples produced using Protocol 3, which was based on raw whey, and fermented with starter culture B. (Average counts of 8.2 log CFU/mL were obtained with starter culture A, and average counts of 8.5 log CFU/mL with starter culture B).

Furthermore, as mentioned previously, the highest levels of microbial diversity were observed in the samples produced using Protocol 3, where fermentation was carried out directly on raw whey without prior heat treatment.

 

Overall, the results pointed to the most effective strategy also being the simplest from a technological perspective: the direct fermentation of raw whey, without prior thermal treatment using starter culture B. This approach maintained high microbial diversity while reducing energy requirements and simplifying the overall process.

An opportunity for the circular economy

Beyond the microbiological results, the broader relevance of this work lies in showing that the role of whey within the cheesemaking chain can be reconsidered.

Rather than being treated as a waste stream associated with management costs, whey can be viewed as a raw material capable of supporting valuable biotechnological processes. Controlled fermentation not only helps stabilise whey but also makes it possible to harness the nutrients it still contains to generate added-value microbial biomass.

Such strategies are closely aligned with the principles of the circular bioeconomy, in which by-products are no longer seen as the end of a production chain, but as the starting point for another. In a context where sustainability and efficient resource use are increasingly important, initiatives of this kind show how microbiology and omics technologies can help turn an environmental challenge into an opportunity for innovation.

 

The PRO2O project (grant agreement No. 00003-BIO2022-48) was funded through the 2022 Bioeconomy Innovation Projects funding programme of the Basque Government’s Department of Economic Development, Sustainability and Environment.

References

[1] Guarner F, Requena T, Marcos A. Consensus statements from the Workshop “Probiotics and Health: Scientific evidence”. Nutr Hosp. 2010 Sep-Oct;25(5):700-4. PMID: 21336423.

[2] Martin, A. J. M., Serebrinsky-Duek, K., Riquelme, E., Saa, P., & Garrido, D. (2023). Microbial interactions and the homeostasis of the gut microbiome: the role of Bifidobacterium. Microbiome Research Reports, 2. https://doi.org/10.20517/mrr.2023.10

[3] González Siso, M. I. (1996). The biotechnological utilization of cheese whey: A review. Bioresource Technology, 57(1), 1–11. https://doi.org/10.1016/0960-8524(96)00036-3

[4] Esneki Zentroa – Leartiker (2022). “El sector quesero en Euskadi 2021”. Available at: El-sector-quesero-en-Euskadi.pdf

[5] Figueroa Pires, A., garcía Marnotes, N., Díaz Rubio, O., Cobos García, A., Dias Pereira, C. (2021). Dairy by-products: A review on the valorization of whey and second cheese whey. Foods, 10: 1067

[6]Neethu, M., Bunt, C., Hussain, M., 2015. Comparison of Microbiological and Probiotic Characteristics of Lactobacilli Isolates from Daity FOod Products and Animal Rumen Contens Microorganims 3, 198-212.

[7] Rama, G.R., Kuhn, D., Beux, S., aciel, M.J., Volken de Souz, C.F., 2019. Potential apllications of dairy why for the production of lactic acid bacteira cultures. Int Dairy J.

[8] Rodriguez-Palacios, 1., Staemplfli, H.R., Duffield, T., Weese, J.S., 009. Isolation of bovine intestinal Lactobacillus plantarum and Pediococcus acidilactici with inhibitory activity against Escherichia coli O157 and F5. J. Appl. Mcrobiol. 106, 393-401

 

The BRTA is a consortium that remains a step ahead of future socio-economic challenges worldwide and in the Basque Autonomous Community; it addresses them through research and technological development, thus projecting itself internationally. The BRTA centres collaborate to generate knowledge and transfer it to Basque society and industry so as to make them more innovative and competitive. The BRTA is an alliance of 17 R&D centres and cooperative research centres with the support of the Basque Government, the SPRI and the Chartered Provincial Councils of Araba, Bizkaia and Gipuzkoa.

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